U.S. patent number 8,921,827 [Application Number 12/622,012] was granted by the patent office on 2014-12-30 for semiconductor nanoparticle-based light-emitting devices and associated materials and methods.
This patent grant is currently assigned to Nanoco Technologies, Ltd.. The grantee listed for this patent is James Harris, Nigel Pickett. Invention is credited to James Harris, Nigel Pickett.
United States Patent |
8,921,827 |
Pickett , et al. |
December 30, 2014 |
Semiconductor nanoparticle-based light-emitting devices and
associated materials and methods
Abstract
Embodiments of the present invention relate to a formulation for
use in the fabrication of a light-emitting device, the formulation
including a population of semiconductor nanoparticles incorporated
into a plurality of discrete microbeads comprising an optically
transparent medium, the nanoparticle-containing medium being
embedded in a host light-emitting diode encapsulation medium. A
method of preparing such a formulation is described. There is
further provided a light-emitting device including a primary light
source in optical communication with such a formulation and a
method of fabricating the same.
Inventors: |
Pickett; Nigel (London,
GB), Harris; James (Manchester, GB) |
Applicant: |
Name |
City |
State |
Country |
Type |
Pickett; Nigel
Harris; James |
London
Manchester |
N/A
N/A |
GB
GB |
|
|
Assignee: |
Nanoco Technologies, Ltd.
(GB)
|
Family
ID: |
40194862 |
Appl.
No.: |
12/622,012 |
Filed: |
November 19, 2009 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20100123155 A1 |
May 20, 2010 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61116142 |
Nov 19, 2008 |
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61116516 |
Nov 20, 2008 |
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Foreign Application Priority Data
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Nov 19, 2008 [GB] |
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0821122.9 |
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Current U.S.
Class: |
257/13; 257/98;
257/9; 257/40; 257/789 |
Current CPC
Class: |
H01L
33/56 (20130101); C09K 11/883 (20130101); C09K
11/02 (20130101); H01L 33/005 (20130101); G01N
33/588 (20130101); H01L 33/04 (20130101); C09K
11/565 (20130101); C09K 11/70 (20130101); B82Y
15/00 (20130101); H01L 33/502 (20130101); H01L
2933/005 (20130101); H01L 2224/48091 (20130101); H01L
2933/0041 (20130101); H01L 33/501 (20130101); H01L
2924/181 (20130101); H01L 2924/181 (20130101); H01L
2924/00012 (20130101); H01L 2224/48091 (20130101); H01L
2924/00014 (20130101) |
Current International
Class: |
H01L
33/00 (20100101) |
Field of
Search: |
;257/98,301,13,9,789,100,40,79 ;977/786,787,834 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1394599 |
|
Feb 2003 |
|
CN |
|
201044521 |
|
May 2007 |
|
CN |
|
1176646 |
|
Jan 2002 |
|
EP |
|
1783137 |
|
May 2007 |
|
EP |
|
1854792 |
|
Nov 2007 |
|
EP |
|
2429838 |
|
Mar 2007 |
|
GB |
|
2005-508493 |
|
Mar 2005 |
|
JP |
|
2005139389 |
|
Jun 2005 |
|
JP |
|
2007-173755 |
|
May 2007 |
|
JP |
|
2007-262215 |
|
Oct 2007 |
|
JP |
|
WO-0224623 |
|
Mar 2002 |
|
WO |
|
WO-0229140 |
|
Apr 2002 |
|
WO |
|
03003015 |
|
Jan 2003 |
|
WO |
|
WO-03099708 |
|
Dec 2003 |
|
WO |
|
WO-2004008550 |
|
Jan 2004 |
|
WO |
|
WO-2004033366 |
|
Apr 2004 |
|
WO |
|
WO-2004065362 |
|
Aug 2004 |
|
WO |
|
WO-2004066361 |
|
Aug 2004 |
|
WO |
|
WO-2005021150 |
|
Mar 2005 |
|
WO |
|
WO-2005106082 |
|
Nov 2005 |
|
WO |
|
WO-2005123575 |
|
Dec 2005 |
|
WO |
|
WO-2006001848 |
|
Jan 2006 |
|
WO |
|
WO-2006017125 |
|
Feb 2006 |
|
WO |
|
WO-2006075974 |
|
Jul 2006 |
|
WO |
|
WO-2006116337 |
|
Nov 2006 |
|
WO |
|
WO-2006118543 |
|
Nov 2006 |
|
WO |
|
WO-2006134599 |
|
Dec 2006 |
|
WO |
|
WO-2007020416 |
|
Feb 2007 |
|
WO |
|
WO-2007049052 |
|
May 2007 |
|
WO |
|
WO-2007060591 |
|
May 2007 |
|
WO |
|
WO-2007065039 |
|
Jun 2007 |
|
WO |
|
WO-2007098378 |
|
Aug 2007 |
|
WO |
|
WO-2007102799 |
|
Sep 2007 |
|
WO |
|
WO-2008013780 |
|
Jan 2008 |
|
WO |
|
WO-2008054874 |
|
May 2008 |
|
WO |
|
WO-2008133660 |
|
Nov 2008 |
|
WO |
|
WO-2009016354 |
|
Feb 2009 |
|
WO |
|
WO-2009040553 |
|
Apr 2009 |
|
WO |
|
WO-2009106810 |
|
Sep 2009 |
|
WO |
|
Other References
Sheng et al. "In-Situ Encapsulation of Quantum Dots into Polymer
Microsphers", Langmuir 22(8):3782-3790 (2006). cited by applicant
.
W. Peter Wuelfing et al., "Supporting Information for Nanometer
Gold Clusters Protected by Surface Bound Monolayers of Thiolated
Poly (ethylene glycol) Polymer Electrolyte" Journal of the American
Chemical Society (XP002529160) (1998). cited by applicant .
International Search Report for PCT/GB2009/000510 mailed Jul. 6,
2010 (16 pages). cited by applicant .
International Search Report for PCT/GB2008/003958 mailed Sep. 4,
2009 (3 pages). cited by applicant .
Banger et al., "Ternary single-source precursors for
polycrystalline thin-film solar cells" Applied Organometallic
Chemistry, 16:617-627, XP002525473 Scheme 1 Chemical Synthesis
(2002). cited by applicant .
D Qi, M Fischbein, M Drndic, S. Selmic, "Efficient
polymer-nanocrystal quantum-dot photodetectors", Appl. Phys. Lett.,
2004, 84, 4295. cited by applicant .
Shen et al., "Photoacoustic and photoelectrochemical
characterization of CdSe-sensitized TiO2 electrodes composed of
nanotubes and nanowires" Thin Solid Films, Elsevier-Sequoia S.A.
Lausanne, CH vol. 499, No. 1-2, Mar. 21, 2006 (Mar. 21, 2006), pp.
299-305, XP005272241 ISSN: 0040-6090. cited by applicant .
Smestad GP, et al., "A technique to compare polythiophene
solid-state dye sensitized TiO2 solar cells to liquid junction
devices" Solar Energy Materials and Solar Cells, Elsevier Science
Publishers, Amsterdam, NL, vol. 76, No. 1, Feb. 15, 2003 (Feb. 15,
2003), pp. 85-105, XP004400821 ISSN: 0927-0248. cited by applicant
.
Chen et al., "Electrochemically synthesized CdS
nanoparticle-modified TiO2 nanotube-array photoelectrodes:
Preparation, characterization, and application to
photoelectrochemical cells" Journal of Photochemistry and
Photobiology, a: Chemistry, Elsevier Sequoia Lausanne, CH, vol.
177, No. 2-3, Jan. 25, 2006 (Jan. 25, 2006), pp. 177-184,
XP005239590 ISSN: 1010-6030. cited by applicant .
Wang, et al., "In situ polymerization of amphiphilic diacetylene
for hole transport in solid state dye-sensitized solar cells"
Organic Electronics, El Sevier, Amsterdam NL, vol. 7, No. 6, Nov.
18, 2006 (Nov. 18, 2006), pp. 546-550, XP005773063 ISSN: 1566-1199.
cited by applicant .
International Search Report and Written Opinion for
PCT/GB2008/001457 mailed Aug. 21, 2008 (14 pages). cited by
applicant .
Richardson et al., "Chemical Engineering: Chemical and Biochemical
Reactors and Process Control," vol. 3, Third Edition, pp. 3-5
(1994). cited by applicant .
Borchert et al., "High Resolution Photoemission STudy of CdSe and
CdSe/ZnS Core-Shell Nanocrystals," Journal of Chemical Physics,
vol. 119, No. 3, pp. 1800-1807 (2003). cited by applicant .
Gaponik et al., "Thiol-Capping of CdTe Nanocrystals: An Alternative
to Organometallic Synthetic Routes," Journal of Physical Chemistry
B, vol. 106, No. 29, pp. 7177-7185 (2002). cited by applicant .
Pickett et al., "Syntheses of Semiconductor Nanoparticles Using
Single-Molecular Precursors," The Chemical Record, vol. 1 pp.
467-479 (2001). cited by applicant .
Hu et al., Solar Cells: From basics to advanced systems.
McGraw-Hill Book Co. pp. 73-74 (1983). cited by applicant .
Talapin et al. "Synthesis of Surface-Modified Colloidal
Semiconductor Nanocrystals and Study of Photoinduced Charge
Separation and Transport in Nanocrystal-Polymer Composites,"
Physica E, vol. 14, pp. 237-241 (2002). cited by applicant .
International Search Report for PCT/GB2009/001928 mailed Dec. 8,
2009 (3 pages). cited by applicant .
International Search Resort for PCT/GB2009/002605 mailed Februar
22, 2010 (3 pages). cited by applicant .
Search Report for GB0813273.0 searched Dec. 8, 2008 (1 page). cited
by applicant .
Search Report for GB0814458.6 searched Dec. 5, 2008 (1 page). cited
by applicant .
Search Report for GB0820101.4 searched Mar. 3, 2009 (1 page). cited
by applicant .
Search Report for GB0821122.9 searched Mar. 19, 2009 (2 pages).
cited by applicant .
Cao, (2005) "Effect of Layer Thickness on the Luminescence
Properties of ZnS/CdS/ZnS quantum dot quantum well", J. of Colloid
and Interface Science 284:516-520. cited by applicant .
Foneberov et al., (2005) "Photoluminescence of tetrahedral
quantum-dot quantum wells" Physica E, 26:63-66. cited by applicant
.
Harrison et al. (2000) "Wet Chemical Synthesis on Spectroscopic
Study of CdHgTe Nanocrystals with Strong Near-Infrared
Luminescence" Mat. Sci and Eng.B69-70:355-360. cited by applicant
.
Agger, J.R. et al., "Growth of Quantum-Confined Indium Phosphide
inside MCM-41," J. Phys. Chem. B (1998) 102, p. 3345. cited by
applicant .
Aldana, J. et al. "Photochemical Instability of CdSe Nanocrystals
Coated by Hydrophilic Thiols", J. Am. Chem. Soc. (2001), 123:
8844-8850. cited by applicant .
Alivisatos, A.P. "Perspectives on the Physical Chemistry of
Semiconductor Nanocrystals", J. Phys. Chem., (1996), 100, pp.
13226-13239. cited by applicant .
Arici et al., "Hybrid Solar Cells Based on Inorganic Nanoclusters
and Conjugated Polymers", Thin Solid Films 451-452 (2004) 612-618.
cited by applicant .
Barron, "Group III Materials: New Phases and Nono-particles with
Applications in Electronics and Optoelectronics," Office of Naval
Research Final Report (1999). cited by applicant .
Battaglia et al., "Colloidal Two-dimensional Systems: CdSe Quantum
Shells and Wells," Angew Chem. (2003) 115:5189. cited by applicant
.
Bawendi, M.G. The Quantum Mechanics of Larger Semiconductor
Clusters ("Quantum Dots"), Annu. Rev. Phys. Chem. (1990), 42:
477-498. cited by applicant .
Berry, C.R. "Structure and Optical Absorption of AgI
Microcrystals", Phys. Rev. (1967) 161:848-851. cited by applicant
.
Bunge, S.D. et al. "Growth and morphology of cadmium chalcogenides:
the synthesis of nanorods, tetrapods, and spheres from CdO and
Cd(O.sub.2CCH.sub.3).sub.2", J. Mater. Chem. (2003) 13: 1705-1709.
cited by applicant .
Castro et al., "Nanocrystalline Chalcopyrite Materials (CuInS.sub.2
and CuInSe.sub.2) via Low-Temperature Pyrolysis of Molecular
Single-Source Precursors", Chem. Mater. (2003) 15:3142-3147. cited
by applicant .
Castro et al., "Synthesis and Characterization of Colloidal CuInS2
Nanoparticles from a Molecular Single-Source Precursors," J. Phys.
Chem. B (2004) 108:12429. cited by applicant .
Chun et al., "Synthesis of CuInGaSe.sub.2 Nanoparticles by
Solvothermal Route", Thin Solid Films 480-481 (2005) 46-49. cited
by applicant .
Contreras et al., "ZnO/ZnS(O,OH)/Cu(In,Ga)Se.sub.2/Mo Solar Cell
with 18:6% Efficiency," from 3d World Conf. on Photovol. Energy
Conv., Late News Paper, (2003) pp. 570-573. cited by applicant
.
Cui et al., "Harvest of near infrared light in PbSe
nanocrystal-polymer hybrid photovoltaic cells," Appl. Physics Lett.
88 (2006) 183111-183111-3. cited by applicant .
Cumberland et al., "Inorganic Clusters as Single-Source Precursors
for Preparation of CdSe, ZnSe, and CdSe/ZnS Nanomaterials"
Chemistry of Materials, 14, pp. 1576-1584, (2002). cited by
applicant .
Dabousi et al., "(CdSe)ZnS Core--Shell Quantum Dots: Synthesis and
Characterization of a Size Series of Highly Luminescent
Nanocrystallites," Jrl. Phys. Chem.,(1997) 101, pp. 9463-9475.
cited by applicant .
Dance et al., "Syntheses, Properties, and Molecular and Crystal
Structures of (Me.sub.4N).sub.4[E.sub.4M.sub.10(SPh).sub.16] (E=S,
Se; M=Zn, Cd): Molecular Supertetrahedral Fragments of the Cubic
Metal Chalcogenide Lattice", J. Am. Chem. Soc. (1984) 106:6285.
cited by applicant .
Daniels et al., "New Zinc and Cadmium Chalcogenide Structured
Nanoparticles," Mat. Res. Soc. Symp. Proc. 789 (2004). cited by
applicant .
Dehnen et al., "Chalcogen-Bridged Copper Clusters," Eur. J. Inorg.
Chem., (2002) pp. 279-317. cited by applicant .
Eisenmann et al., "New Phosphido-bridged Multinuclear Complexes of
Ag and Zn," Zeitschrift fur anorganische und allgemeine Chemi
(1995). (1 page--abstract). cited by applicant .
Eychmuller, A. et al. "A quantum dot quantum well: CdS/HgS/CdS",
Chem. Phys. Lett. 208, pp. 59-62 (1993). cited by applicant .
Fendler, J.H. et al. "The Colloid Chemical Approach to
Nanostructured Materials", Adv. Mater. (1995) 7: 607-632. cited by
applicant .
Gao, M. et al. "Synthesis of PbS Nanoparticles in Polymer
Matrices", J. Chem. Soc. Commun. (1994) pp. 2779-2780. cited by
applicant .
Gou et al., "Shape-Controlled Synthesis of Ternary Chalcogenide
ZnIn.sub.2S.sub.4 and CuIn(S,Se).sub.2 Nano-/Microstructures via
Facile Solution Route", J. Am. Chem. Soc. (2006) 128:7222-7229.
cited by applicant .
Gur et al., "Air stable all-inorganic nanocrystal solar cells
processed from solution," Lawrence Berkele Natl. Lab., Univ. of
California, paper LBNL-58424 (2005). cited by applicant .
Gurin, "Nanoparticles of Ternary Semiconductors in Colloids
Low-Temperature Formation and Quantum Size Effects", Colloids Surf.
A (1998) 142:35-40. cited by applicant .
Guzelian, A. et al. "Colloidal chemical synthesis and
characterization of InAs nanocrystal quantum dots", Appl. Phys.
Lett. (1996) 69: 1432-1434. cited by applicant .
Guzelian, A. et al., "Synthesis of Size-Selected,
Surface-Passivated InP Nanocrystals", J. Phys. Chem. (1996) 100:
7212. cited by applicant .
Hagfeldt, A. et al. "Light-induced Redox Reactions in
Nanocrystalline Systems", Chem. Rev. (1995) 95: 49-68. cited by
applicant .
Henglein, A. "Small-Particle Research: Physicochemical Properties
of Extremely Small Colloidal Metal and Semiconductor Particles",
Chem Rev. (1989) 89: 1861-1873. cited by applicant .
Hirpo et al., "Synthesis of Mixed Copper-Indium Chalcogenolates.
Single-Source Precursors for the Photovoltaic Materials CuInQ2 (Q =
S, Se)," J. Am. Chem. Soc. (1993) 115:1597. cited by applicant
.
Hu et al., "Hydrothermal Preparation of CuGaS.sub.2 Crystallites
with Different Morphologies", Sol. State Comm. (2002) 121:493-496.
cited by applicant .
Huang et al., "Bio-Inspired Fabrication of Antireflection
Nanostructures by Replicating Fly Eyes", Nanotechnology (2008) vol.
19. cited by applicant .
International Search Report for PCT/GB2005/001611 mailed Sep. 8,
2005 (5 pages). cited by applicant .
International Search Report for PCT/GB2006/003028 mailed Jan. 22,
2007 (5 pages). cited by applicant .
Jegier, J.A. et al. "Poly(imidogallane): Synthesis of a Crystalline
2-D Network Solid and Its Pyrolysis to Form Nanocrystalline Gallium
Nitride in Supercritical Ammonia", Chem. Mater. (1998) 10:
2041-2043. cited by applicant .
Jiang et al., "Elemental Solvothermal Reaction to Produce Ternary
Semiconductor CuInE.sub.2 (E=Se) Nnaorods", Inorg. Chem. (2000)
39:2964-2965. cited by applicant .
Kaelin el al., "CIS and CIGS layers from selenized nanoparticle
precursors," Thin Solid Films 431-432 (2003) pp. 58-62. cited by
applicant .
Kapur et al., "Non-Vacuum processing of CuIn.sub.1-xGaxSe.sub.2
solar cells on rigid and flexible substrates using nanoparticle
precursor inks," Thin Solid Films 431-432 (2003) pp. 53-57. cited
by applicant .
Kher, S. et al. "A Straightforward, New Method for the Synthesis of
Nanocrystalline GaAs and GaP", Chem. Mater. (1994) 6: 2056-2062.
cited by applicant .
Kim et al. "Engineering InAsxP1-x/InP/ZnSe III-V Alloyed Core-Shell
Quantum Dots for the Near-Infrared" JACS Articles published on web
Jul. 8, 2005. cited by applicant .
Kim et al "Synthesis of CuInGaSe.sub.2 Nanoparticles by Low
Temperature Colloidal Route", J. Mech. Sci. Tech. (2005)
19:2085-2090. cited by applicant .
Law et al., "Nanowire dye-sensitized solar cells," Nature Mater.
(2005) vol. 4 pp. 455-459. cited by applicant .
Li et al., "Synthesis by a Solvothermal Route and Characterization
of CuInSe.sub.2 Nanowhiskers and Nanoparticles", Adv. Mat. (1999)
11:1456-1459. cited by applicant .
Lieber, C. et al. "Understanding and Manipulating Inorganic
Materials with Scanning Probe Microscopes", Angew. Chem. Int. Ed.
Engl. (1996) 35: 687-704. cited by applicant .
Little et al., "Formation of Quantum-dot quantum-well
heteronanostructures with large lattice mismatch: Zn/CdS/ZnS," 114
J. Chem. Phys. 4 (2001). cited by applicant .
Lover, T. et al. "Preparation of a novel CdS nanocluster material
from a thiophenolate-capped CdS cluster by chemical removal of SPh
ligands", J. Mater. Chem. (1997) 7(4): 647-651. cited by applicant
.
Lu et al., "Synthesis of Nanocrystalline CuMS.sub.2 (M=In or Ga)
Through a Solvothermal Process", Inorg. Chem. (2000) 39:1606-1607.
cited by applicant .
Malik et al., "A Novel Route for the Preparation of CuSe and
CuInSe.sub.2 Nanoparticles", Adv. Mat., (1999) 11:1441-1444. cited
by applicant .
Materials Research Society Symposium Proceedings Quantum Dots,
Nanoparticles and Nanowires, 2004, ISSN: 0272-9172. cited by
applicant .
Matijevic, E. "Production of Mondispersed Colloidal Particles",
Ann. Rev. Mater. Sci. (1985) 15: 483-518. cited by applicant .
Matijevic, E., "Monodispersed Colloids: Art and Science", Langmuir
(1986) 2:12-20. cited by applicant .
Mekis, I. et al., "One-Pot Synthesis of Highly Luminescent CdSe/CdS
Core-Shell Nanocrystals via Organometallic and "Greener" Chemical
Approaches", J. Phys. Chem. B. (2003) 107:7454-7462. cited by
applicant .
Mews et al., "Preparation, Characterization, and Photophysics of
the Quantum Dot Quantum Well System CdS/HgS/CdS", J. Phys. Chem.
(1994) 98:934. cited by applicant .
Mi i et al., "Synthesis and Characterization of InP, GaP, and
GaInP.sub.2 Quantum Dots", J. Phys. Chem. (1995) pp. 7754-7759.
cited by applicant .
Milliron et al., "Electroactive Surfactant Designed to Mediate
Electron Transfer between CdSe Nanocrystals and Organic
Semicondictors," Adv. Materials (2003) 15, No. 1, pp. 58-61. cited
by applicant .
Murray, C.B. et al., "Synthesis and Characterization of Nearly
Monodisperse CdE (E = S, Se, Te) Semiconductor Nanocrystallites",
J. Am. Chem. Soc. (1993) 115 (19) pp. 8706-8715. cited by applicant
.
Muller et al., "From Giant Molecular Clusters and Precursors to
Solid-state Structures," Current Opinion in Solid State and
Materials Science, 4 (Apr. 1999) pp. 141-153. cited by applicant
.
Nairn et al., "Preparation of Ultrafine Chalcopyrite Nanoparticles
via the Photochemical Decomposition of Molecular Single-Source
Precursors", Nano Letters (2006) 6:1218-1223. cited by applicant
.
Nazeeruddin et al., "Conversion of Light to Electricity by
cis-X.sub.2Bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II)
Charge-Transfer Sensitizers (X= C1-, Br-, I-, CN-, and SCN-)on
Nanocrystalline TiO.sub.2 Electrodes," J. Am. Chem. Soc. (1993)
115:6382-6390. cited by applicant .
Nazeeruddin et al., "Engineering of Efficient Panchromatic
Sensitizers for Nanocrystalline TiO.sub.2-Based Solar Cells," J.
Am. Chem. Soc. (2001) 123:1613-1624. cited by applicant .
Nielsch et al., "Uniform Nickel Deposition into Ordered Alumina
Pores by Pulsed Electrodeposition", Advanced Materials, 2000 vol.
12, No. 8, pp. 582-586. cited by applicant .
O'Brien et al., "The Growth of Indium Selenide Thin Films from a
Novel Asymmetric Dialkydiselenocarbamate," 3 Chem, Vap. Depos. 4,
pp. 227 (1979). cited by applicant .
Olshaysky, M.A., et al. "Organometallic Synthesis of GaAs
Crystallites Exhibiting Quantum Confinement", J. Am. Chem. Soc.
(1990) 112: 9438-9439. cited by applicant .
Olson et al., "Effect of Polymer Processing on the Performance of
Poly(3-hexylthiophene)/ZnO Nnaorod Photovoltaic Devices", J. Phys.
Chem. C. (2007) 111:16640-16645. cited by applicant .
Patent Act 1977 Search Report under Section 17 for Application No.
GB0522027.2 dated Jan. 27, 2006 (1 page). cited by applicant .
Patent Act 1977 Search Report under Section 17 for Application No.
GB0606845.6 dated Sep. 14, 2006. cited by applicant .
Patent Act 1977 Search Report under Section 17 for Application No.
GB0719073.9. cited by applicant .
Patent Act 1977 Search Report under Section 17 for Application No.
GB0719075.4. cited by applicant .
Patent Act 1977 Search Report under Section 17 for Application No.
GB0723539,3 dated Mar. 27, 2008 (1 page). cited by applicant .
Patents Act 1977: Search Report under Section 17 for Application
No. GB0409877.8 dated Oct. 7, 2004 (2 pages). cited by applicant
.
Peng et al., "Kinetics of I-VI and III-V Colloidal Semiconductor
Nanocrystal Growth: "Focusing" os Size Distributions", J. Am. Chem.
Soc., (1998) 129: 5343-5344. cited by applicant .
Peng et al., "Mechanisms of the Shape Evolution of CdSe
Nanocrystals", J. Am. Chem. Soc. (2001) 123:1389. cited by
applicant .
Peng et al., "Shape control of CdSe nanocrystals", Nature, (2000)
vol. 404, No. 6773, pp. 59-61. cited by applicant .
Pradhan, N. et al. "Single-Precursor, One-Pot Versatile Synthesis
under near Ambient Conditions of Tunable, Single and Dual Band
Flourescing Metal Sulfide Nanoparticles", J. Am. Chem. Soc. (2003)
125: 2050-2051. cited by applicant .
Qi et al., "Efficient polymer-nanocrystal quantum-dot
photodetectors," Appl. Physics Lett. 86 (2005) 093103-093103-3.
cited by applicant .
Qu, L. et al. "Alternative Routes toward High Quality CdSe
Nanocrystals", Nano Lett. (2001) vol. 1, No. 6, pp. 333-337. cited
by applicant .
Rao et al. (2004) "The Chemistry of Nanomaterials: Synthesis,
Properties and Applications" p. 443. cited by applicant .
Robel et al., "Quantum Dot Solar Cells. Harvesting Light Energy
with CdSe Nanocrystals Molecularly Linked to Mesoscopic TiO.sub.2
Films," J. Am. Chem. Soc. (2006) 128: 2385-2393. cited by applicant
.
Salata, O.V. et al. "Uniform GaAs quantum dots in a polymer
matrix", Appl. Phys. Letters (1994) 65(2): 189-191. cited by
applicant .
Sercel, P.C. et al. "Nanometer-scale GaAs clusters from
organometallic percursors", Appl. Phys. Letters (1992) 61: 696-698.
cited by applicant .
Shulz et al., "Cu-In-Ga-Se Nanoparticle Colloids as Spray
Deposition Precursors for Cu(In,Ga)Se.sub.2 Solar Cell Materials",
J. Elect. Mat. (1998) 27:433-437. cited by applicant .
Steigerwald, M.L. et al. "Semiconductor Crystallites: A Class of
Large Molecules", Acc. Chem. Res. (1990) 23: 183-188. cited by
applicant .
Stroscio, J.A. et al. "Atomic and Molecular Manipulation with the
Scanning Tunneling Microscope", Science (1991), 254: 1319-1326.
cited by applicant .
Timoshkin, "Group 13 imido metallanes and their heavier analogs
[RMYR'].sub.n (M=Al, Ga, In; Y=N, P, As, Sb)," Coordination
Chemistry Reviews (2005). cited by applicant .
Trinidade et al., "A Single Source Spproach to the Synthesis of
CdSe Nanocrystallites", Advanced Materials, (1996) vol. 8, No. 2,
pp. 161-163. cited by applicant .
Trinidade et al., "Nanocrystalline Seminconductors: Synthesis,
Properties, and Perspectives", Chemistry of Materials, (2001) vo1.
13, No. 11, pp. 3843-3858. cited by applicant .
Vayssieres et al., "Highly Ordered SnO.sub.2 Nanorod Arrays from
Controlled Aqueous Growth," Angew. Chem. Int. Ed. (2004) 43:
3666-3670. cited by applicant .
Vittal, "The chemistry of inorganic and organometallic compounds
with adameantane-like structures," Polyhedron, vol. 15, No. 10, pp.
1585-1642 (1996). cited by applicant .
Wang Y. et al. "PbS in polymers, From molecules to bulk solids", J.
Chem. Phys. (1987) 87: 7315-7322. cited by applicant .
Weller, H. "Colloidal Semiconductor Q-Particles: Chemistry in the
Transition Region Between Solid State and Molecules", Angew. Chem.
Int. Ed. Engl. (1993) 32: 41-53. cited by applicant .
Weller, H. "Quantized Semiconductor Particles: A Novel State of
Mater for Materials Science", Adv. Mater. (1993) 5: 88-95. cited by
applicant .
Wells, R.L. et al. "Synthesis of Nanocrystalline Indium Arsenide
and Indium Phosphide from Indium(III) Halides and Tris
(trimethylsilyl)pnicogens. Synthesis, Characterization, and
Decomposition Behavior of I3In-P(SiMe3)3"Chem. Mater. (1995)
7:793-800. cited by applicant .
Xiao et al., "A Mild Solvothermal Route to Chalcopyrite Quaternary
Semiconductor CuIn(Se.sub.xS.sub.1-x).sub.2 Nanocrystallites", J.
Mater. Chem. (2001) 11:1417-1420. cited by applicant .
Xie et al. "Synthesis and Characterization of Highly Luminescent
CdSe-Core CdS/Zn0.5Cd0.5S/ZnS Multishell Nanocrystals" JACS
Articles published on web Apr. 29, 2005. cited by applicant .
Yang et al., "Studies of Electrochemical Synthesis of Ultrathin ZnO
Nanorod/Nanobelt Arrays on Zn Substrates in Alkaline Solutions of
Amine-Alcohol Mixtures", Crystal Growth & Design (2007)
12:2562-2567. cited by applicant .
Yu et al., "Polymer Photovoltaic Cells: Enhanced Efficiencies via a
Network of Internal Donor-Acceptor Heterojunctions," 270 Science
5243 (1995) , pp. 1789-1791. cited by applicant .
Zhong et al, "Composition-Tunable Zn.sub.xCu.sub.1-xSe Nanocrytals
with High Luminescence and Stability", Jrl Amer. Chem. Soc. (2003).
cited by applicant .
Zhong et al., "A Facile Route to Synthesize Chalcopyrite CuInSe2
Nanocrystals in Non-Coordinating Solvent", Nanotechnology 18 (2007)
025602. cited by applicant.
|
Primary Examiner: Luu; Chuong A
Attorney, Agent or Firm: Wong, Cabello, Lutsch, Rutherford
& Brucculeri LLP.
Parent Case Text
RELATED APPLICATIONS
This application claims the benefit of and priority to U.S.
Provisional Patent Application Ser. No. 61/116,142 filed Nov. 19,
2008, U.S. Provisional Patent Application Ser. No. 61/116,516 filed
Nov. 20, 2008, and GB 0821122.9 filed Nov. 19, 2008, the
disclosures of which are incorporated herein by reference in their
entireties.
Claims
What is claimed is:
1. A formulation for use in the fabrication of a light-emitting
device, said formulation comprising: a population of semiconductor
quantum dots dispersed into a plurality of microbeads, the
microbeads comprising an optically transparent medium, said
microbeads being embedded in a host light-emitting diode (LED)
encapsulation medium, wherein the semiconductor quantum dots
comprise surface-bound ligands selected to provide compatibility
with the transparent medium.
2. A formulation according to claim 1, wherein each of said
microbeads incorporates a plurality of said dispersed semiconductor
quantum dots.
3. A formulation according to claim 2, wherein said microbeads
possess an average diameter of around 20 nm to around 0.5 mm.
4. A formulation according to claim 1, wherein said optically
transparent medium comprises a material selected from the group
consisting of a polymer, a resin, a monolith, a glass, a sol gel,
an epoxy, a silicone, and a (meth)acrylate.
5. A formulation according to claim 1, wherein said optically
transparent medium comprises a material selected from the group
consisting of poly(methyl(meth)acrylate), poly(ethylene glycol
dimethacrylate), poly(vinyl acetate), poly(divinyl benzene),
poly(thioether), silica, polyepoxide, and combinations thereof.
6. A formulation according to claim 1, wherein said optically
transparent medium comprises a material selected from the group
consisting of a copolymer of poly(methyl(meth)acrylate),
poly(ethylene glycol dimethacrylate) and poly(vinyl acetate);
polystyrene, polydivinyl benzene and a polythiol; and a 30
copolymer of 3-(trimethoxysilyl)propylmethacrylate and tetramethoxy
silane.
7. A formulation according to claim 1, wherein at least some of the
microbeads include a core comprising a first optically transparent
medium and one or more outer layers of the same or one or more
different optically transparent media deposited on said core.
8. A formulation according to claim 7, wherein said semiconductor
quantum dots are confined to the core of the microbeads or are
dispersed throughout the core and/or one or more of the outer
layers of the microbeads.
9. A formulation according to claim 1, wherein said LED
encapsulation medium comprises a material selected from the group
consisting of a polymer, an epoxy, a silicone, and a
(meth)acrylate.
10. A formulation according to claim 1, wherein said LED
encapsulation medium is selected from the group consisting of
silica glass, silica gel, siloxane, sol gel, hydrogel, agarose,
cellulose, epoxy, polyether, polyethylene, polyvinyl,
poly-diacetylene, polyphenylene-vinylene, polystyrene, polypyrrole,
polyimide, polyimidazole, polysulfone, poly thiophene,
polyphosphate, poly(meth)acrylate, polyacrylamide, polypeptide,
polysaccharide, and combinations thereof.
11. A formulation according to claim 1, wherein said semiconductor
quantum dots contain ions selected from group consisting of groups
11, 12, 13, 14, 15 and 16 of the periodic table, transition metal
ions and d-block metal ion.
12. A formulation according to claim 1, wherein said semiconductor
quantum dots contain one or more semiconductor materials selected
from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP,
InAs, InSb, AlP, Al.sub.2S.sub.3, AlAs, AlSb, GaN, GaP, GaAs, GaSb,
PbS, PbSe, Si, Ge, MgS, MgSe, MgTe, and combinations thereof.
13. The formulation of claim 1, wherein the surface-bound ligands
are polymerizable monomers.
14. The formulation of claim 1, wherein the surface-bound ligands
comprise functional groups capable of associating with the
optically transparent medium.
Description
FIELD OF THE INVENTION
The present invention relates to semiconductor nanoparticle--based
light-emitting devices and associated materials and methods.
Particularly, but not exclusively, the present invention relates to
formulations for use in the fabrication of quantum dot-based
light-emitting devices and methods for producing such devices
employing such formulations.
BACKGROUND
Light-emitting diodes (LEDs) are becoming more important to modern
day life and it is envisaged that they will become one of the major
applications in many forms of lighting such as automobile lights,
traffic signals, general lighting, liquid crystal display (LCD)
backlighting and display screens. Currently, LED devices are
typically made from inorganic solid-state compound semiconductors,
such as AlGaAs (red), AlGaInP (orange-yellow-green), and AlGaInN
(green-blue). However, using a mixture of the available solid-state
compound semiconductors, solid-state LEDs that emit white light
cannot be produced. Moreover, it is difficult to produce "pure"
colors by mixing solid-state LEDs of different frequencies.
Therefore, currently the main method of color mixing to produce a
required color, including white, is to use a combination of
phosphorescent materials that are placed on top of the solid-state
LED whereby the light from the LED (the "primary light") is
absorbed by the phosphorescent material and then re-emitted at a
different frequency (the "secondary light"), i.e., the
phosphorescent materials down convert the primary light to the
secondary light. Moreover, the use of white LEDs produced by
phosphor down-conversion leads to lower cost and simpler device
fabrication than a combination of solid-state red-green-blue
LEDs.
Current phosphorescent materials used in down converting
applications absorb UV or mainly blue light and convert it to
longer wavelengths, with most phosphors currently using trivalent
rare-earth doped oxides or halophosphates. White emission can be
obtained by blending phosphors that emit in the blue, green and red
regions with that of a blue or UV emitting solid-state device.
i.e., a blue light-emitting LED plus a green phosphor such as,
SrGa.sub.2S.sub.4:Eu.sub.2.sup.+, and a red phosphor such as,
SrSiEu.sub.2.sup.+ or a UV light-emitting LED plus a yellow
phosphor such as, Sr.sub.2P.sub.2O.sub.7:Eu.sub.2.sup.+;
Mu.sub.2.sup.+, and a blue-green phosphor. White LEDs can also be
made by combining a blue LED with a yellow phosphor, however, color
control and color rendering may be poor when using this methodology
due to lack of tunability of the LEDs and the phosphor. Moreover,
conventional LED phosphor technology uses down converting materials
that have poor color rendering (i.e., color rendering index
(CRI)<75).
SUMMARY
There has been substantial interest in exploiting the properties of
compound semiconductors consisting of particles with dimensions in
the order of 2-50 nm, often referred to as quantum dots (QDs) or
nanocrystals. These materials are of commercial interest due to
their size-tuneable electronic properties that can be exploited in
many commercial applications such as optical and electronic devices
and other applications, including biological labelling,
photovoltaics, catalysis, biological imaging, LEDs, general space
lighting and electroluminescent displays, amongst many new and
emerging applications.
The most studied of semiconductor materials have been the
chalcogenides II-VI materials namely ZnS, ZnSe, CdS, CdSe, CdTe;
most noticeably CdSe due to its tuneability over the visible region
of the spectrum. Reproducible methods for the large scale
production of these materials have been developed from "bottom up"
techniques, whereby particles are prepared atom-by-atom, i.e., from
molecules to clusters to particles, using "wet" chemical
procedures.
Two fundamental factors, both related to the size of the individual
semiconductor nanoparticle, are responsible for their unique
properties. The first is the large surface-to-volume ratio; as a
particle becomes smaller, the ratio of the number of surface atoms
to those in the interior increases. This leads to the surface
properties playing an important role in the overall properties of
the material. The second factor is, with many materials including
semiconductor nanoparticles, that there is a change in the
electronic properties of the material with size, moreover, because
of quantum confinement effects the band gap gradually becomes
larger as the size of the particle decreases. This effect is a
consequence of the confinement of an `electron in a box` giving
rise to discrete energy levels similar to those observed in atoms
and molecules, rather than a continuous band as observed in the
corresponding bulk semiconductor material. Thus, for a
semiconductor nanoparticle, because of the physical parameters, the
"electron and hole", produced by the absorption of electromagnetic
radiation, a photon, with energy greater then the first excitonic
transition, are closer together than they would be in the
corresponding macrocrystalline material. Moreover, the Coulombic
interaction cannot be neglected. This leads to a narrow bandwidth
emission that depends upon the particle size and composition of the
nanoparticle material. Thus, quantum dots have higher kinetic
energy than the corresponding macrocrystalline material and
consequently the first excitonic transition (band gap) increases in
energy with decreasing particle diameter.
Core semiconductor nanoparticles that consist of a single
semiconductor material along with an outer organic passivating
layer tend to have relatively low quantum efficiencies due to
electron-hole recombination occurring at defects and dangling bonds
situated on the nanoparticle surface that may lead to non-radiative
electron-hole recombinations. One method to eliminate defects and
dangling bonds on the inorganic surface of the quantum dot is to
grow a second inorganic material, having a wider band-gap and small
lattice mismatch to that of the core material epitaxially on the
surface of the core particle, to produce a "core-shell" particle.
Core-shell particles separate any carriers confined in the core
from surface states that would otherwise act as non-radiative
recombination centres. One example is a ZnS shell grown on the
surface of a CdSe core. Another approach is to prepare a core-multi
shell structure where the "electron-hole" pair is completely
confined to a single shell layer consisting of a few monolayers of
a specific material such as a quantum dot-quantum well structure.
Here, the core is of a wide band gap material, followed by a thin
shell of narrower band gap material, and capped with a further wide
band gap layer, such as CdS/HgS/CdS grown using substitution of Hg
for Cd on the surface of the core nanocrystal to deposit just a few
monolayers of HgS that is then over grown by a monolayer of CdS.
The resulting structures exhibit clear confinement of photo-excited
carriers in the HgS layer. To add further stability to quantum dots
and help to confine the electron-hole pair one of the most common
approaches is to epitaxially grow a compositionally graded alloy
layer on the core. This can help to alleviate strain that could
otherwise led to defects. Moreover, for a CdSe core, in order to
improve structural stability and quantum yield, rather than growing
a shell of ZnS directly on the core a graded alloy layer of
Cd.sub.1-xZn.sub.xSe.sub.1-yS.sub.y can be used. This has been
found to greatly enhance the photoluminescence emission of the
quantum dots.
Doping quantum dots with atomic impurities is an efficient way also
of manipulating the emission and absorption properties of the
nanoparticle. Procedures for doping of wide band gap materials,
such as zinc selenide and zinc sulfide, with manganese and copper
(ZnSe:Mn or ZnS:Cu), have been developed. Doping with different
luminescence activators in a semiconducting nanocrystal can tune
the photoluminescence and electroluminescence at energies even
lower than the band gap of the bulk material whereas the quantum
size effect can tune the excitation energy with the size of the
quantum dots without having a significant change in the energy of
the activator related emission.
Rudimentary quantum dot-based light-emitting devices have been made
by embedding colloidally produced quantum dots in an optically
clear LED encapsulation medium, typically a silicone or an
acrylate, that is then placed on top of a solid-state LED. The use
of quantum dots potentially has some significant advantages over
the use of the more conventional phosphors, such as the ability to
tune the emission wavelength, strong absorption properties, and low
scattering if the quantum dots are mono-dispersed.
For the commercial application of quantum dots in next-generation
light-emitting devices, the quantum dots are preferably
incorporated into the LED encapsulating material while remaining as
fully mono-dispersed as possible and without significant loss of
quantum efficiency. The methods developed to date are problematic,
not least because of the nature of current LED encapsulants.
Quantum dots can agglomerate when formulated into current LED
encapsulants thereby reducing the optical performance of the
quantum dots. Moreover, once the quantum dots are incorporated into
the LED encapsulant, oxygen can migrate through the encapsulant to
the surfaces of the quantum dots, which can lead to photo-oxidation
and, as a result, a drop in quantum yield (QY). Although reasonably
efficient quantum dot-based light-emitting devices can be
fabricated under laboratory conditions building on current
published methods, there remain significant challenges to develop
materials and methods for fabricating quantum dot-based
light-emitting devices under commercial conditions on an
economically viable scale.
In some embodiments, the present invention may obviate or mitigate
one or more of the problems with current methods for fabricating
semiconductor nanoparticle-based light-emitting devices.
Embodiments of the present invention may feature a formulation for
use in the fabrication of a light-emitting device. The formulation
may include a population of semiconductor nanoparticles
incorporated into a plurality of discrete microbeads comprising an
optically transparent medium, the nanoparticle-containing medium
being embedded in a host light-emitting diode (LED) encapsulation
medium.
One or more of the following features may be included. Each of the
discrete microbeads may incorporate a plurality of the
semiconductor nanoparticles. The microbeads may possess an average
diameter of around 20 nm to around 0.5 mm. The optically
transparent medium may include a material such as a polymer, a
resin, a monolith, a glass, a sol gel, an epoxy, a silicone, and/or
a (meth)acrylate. The optically transparent medium may include a
poly(methyl(meth)acrylate), poly(ethylene glycol di methacrylate),
poly(vinyl acetate), poly(divinyl benzene), poly(thioether),
silica, polyepoxide, and/or combinations thereof. Alternatively,
the optically transparent medium may include a copolymer of
poly(methyl(meth)acrylate), poly(ethylene glycol dimethacrylate)
and poly(vinyl acetate); polystyrene, polydivinyl benzene and a
polythiol; and/or a copolymer of
3-(trimethoxysilyl)propylmethacrylate and tetramethoxy silane.
At least some of the nanoparticle-containing microbeads may include
a core including a first optically transparent medium and one or
more outer layers of the same or one or more different optically
transparent media deposited on the core. The semiconductor
nanoparticles may be confined to the core of the microbeads or may
be dispersed throughout the core and/or one or more of the outer
layers of the microbeads.
The LED encapsulation medium may include a polymer, an epoxy, a
silicone, and/or a (meth)acrylate. The LED encapsulation medium may
be, e.g., silica glass, silica gel, siloxane, sol gel, hydrogel,
agarose, cellulose, epoxy, polyether, polyethylene, polyvinyl,
poly-diacetylene, polyphenylene-vinylene, polystyrene, polypyrrole,
polyimide, polyimidazole, polysulfone, polythiophene,
polyphosphate, poly(meth)acrylate, polyacrylamide, polypeptide,
polysaccharide, and/or combinations thereof.
The semiconductor nanoparticles may contain ions selected from
group 11, 12, 13, 14, 15 and/or 16 of the periodic table, or the
quantum dots may contain one or more types of transition metal ion
or d-block metal ion. The semiconductor nanoparticles may contain
one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, InSb,
AlP, AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, Ge, MgS,
MgSe, MgTe, and combinations thereof.
Some embodiments of the present invention may feature a method for
preparing a formulation for use in the fabrication of a
light-emitting device. The method may include incorporating a
population of semiconductor nanoparticles into a plurality of
discrete microbeads comprising an optically transparent medium. The
nanoparticle-containing medium may be embedded into a host
light-emitting diode encapsulation material.
One or more of the following features may be included. The
incorporation of semiconductor nanoparticles into the optically
transparent medium may include the polymerisation of one or more
polymerisable monomers from which the optically transparent medium
is to be formed in the presence of at least a portion of the
semiconductor nanoparticles to be incorporated into the optically
transparent medium. The polymerisation may be carried out by, e.g.,
suspension, dispersion, emulsion, living, anionic, cationic, RAFT,
ATRP, bulk, ring closing metathesis, and/or ring opening
metathesis. Alternatively, the polymerisation may be suspension
polymerisation involving thermal curing of the one or more
polymerisable monomers.
The polymerisable monomers may include methyl(meth)acrylate,
ethylene glycol dimethacrylate, and vinyl acetate.
The incorporation of semiconductor nanoparticles into the optically
transparent medium may include physical attachment of at least a
portion of the semiconductor nanoparticles to prefabricated
polymeric beads. The attachment may be achieved by, e.g.,
immobilisation of the portion of the semiconductor nanoparticles
within the polymer matrix of the prefabricated polymeric beads, or
by chemical, covalent, ionic, or physical connection between the
portion of semiconductor nanoparticles and the prefabricated
polymeric beads.
The prefabricated polymeric beads may include polystyrene,
polydivinyl benzene, and a polythiol.
The nanoparticle-containing medium may be embedded into the host
light-emitting diode encapsulation material by mixing the
nanoparticle-containing medium with the encapsulation material
until the nanoparticle-containing medium is substantially evenly
dispersed throughout the encapsulation medium.
The semiconductor nanoparticles may be produced by converting a
nanoparticle precursor composition to the material of the
nanoparticles in the presence of a molecular cluster compound under
conditions permitting seeding and growth of the nanoparticles on
the cluster compound.
The semiconductor nanoparticles incorporate first and second ions
and the nanoparticle precursor composition comprises separate first
and second nanoparticle precursor species containing said first and
second ions respectively for incorporation into the growing
nanoparticles.
The semiconductor nanoparticles may incorporate first and second
ions, and the nanoparticle precursor composition may include a
single molecular species containing the first and second ions for
incorporation into the growing nanoparticles.
Still other embodiments of the invention may feature a
light-emitting device. The light-emitting device may include a
primary light source in optical communication with a formulation
including a population of semiconductor nanoparticles incorporated
into a plurality of discrete microbeads comprising an optically
transparent medium. The nanoparticle-containing medium may be
embedded in a host light-emitting diode encapsulation medium.
The primary light source may be, e.g., a light-emitting diode, a
laser, an arc lamp, and/or a black-body light source. The
formulation may include a population of semiconductor nanoparticles
incorporated into a plurality of discrete microbeads comprising an
optically transparent medium, the nanoparticle-containing medium
being embedded in a host light-emitting diode encapsulation
medium.
Yet other embodiments of the invention may feature a method of
fabricating a light-emitting device. The method includes providing
a population of semiconductor nanoparticles in a plurality of
discrete microbeads comprising an optically transparent medium. The
nanoparticle-containing medium is embedded in a host light-emitting
diode encapsulation material to produce a nanoparticle-containing
formulation. The formulation is deposited onto a primary light
source such that the primary light source is in optical
communication with the population of semiconductor
nanoparticles.
The encapsulation medium may be cured after being deposited onto
the primary light source. The formulation may include a population
of semiconductor nanoparticles incorporated into a plurality of
discrete microbeads comprising an optically transparent medium, the
nanoparticle-containing medium being embedded in a host
light-emitting diode (LED) encapsulation medium.
BRIEF DESCRIPTION OF FIGURES
Embodiments of the present invention is illustrated with reference
to the following non-limiting examples and figures in which:
FIG. 1 is a schematic drawing depicting a quantum dot-based
light-emitting device according to an aspect of the present
invention;
FIG. 2 is a graph illustrating white light from a conventional
light-emitting device employing a blue emitting LED in combination
with a broad emitting green-orange phosphor;
FIGS. 3a and 3b include simulated spectra relating to theoretical
white light-emitting devices with FIG. 3a being a spectra for a
trichromatic-dual quantum dot light-emitting device; and FIG. 3b
being a spectra for a quadchromatic-triple quantum dot
light-emitting device. Note: all spectra have 1931 CIE x,y
coordinates of 0.311, 0.324 and color rendering index increases
from a to b;
FIG. 4 is a 2.degree. CIE 1931 chromaticity diagram;
FIG. 5 is a 2.degree. CIE 1931 color matching diagram matching
functions x, y, z;
FIG. 6 is a schematic representation of a QD-bead-based
light-emitting device according to an aspect of the present
invention employing multi-colored, multiple quantum dot types in
each bead such that each bead emits white secondary light;
FIG. 7 is a schematic representation of a QD-bead-based
light-emitting device according to an aspect of the present
invention employing multi-colored, multiple quantum dot types in
different beads such that each bead contains a single quantum dot
type emitting a single color, a mixture of the beads combining to
produce white secondary light;
FIG. 8 is a schematic representation of a QD-bead-based
light-emitting device according to an aspect of the present
invention employing singly colored, single quantum dot type in all
beads such that a mixture of the beads emits a single color of
secondary light (in this case, red light); and
FIG. 9 is a plot of efficacy and quantum dot-photoluminescence
intensity expressed as a percentage of the initial value versus
time for the two devices described in the Comparative Example
below.
DETAILED DESCRIPTION
A first aspect of the present invention provides a formulation for
use in the fabrication of a light-emitting device, the formulation
including a population of semiconductor nanoparticles incorporated
into a plurality of discrete microbeads comprising an optically
transparent medium, the nanoparticle-containing medium being
embedded in a host light-emitting diode (LED) encapsulation
medium.
Embodiments of the current invention provide a semiconductor
nanoparticle formulation for use in the fabrication of
light-emitting devices, preferably with the devices incorporating
an LED as a primary light source and the semiconductor
nanoparticles as a secondary light source. In a preferred
embodiment, the formulation contains one or more quantum dots
incorporated into a plurality of polymeric beads embedded or
entrapped within a host LED encapsulation material such as a
silicone, an epoxy resin, a (meth)acrylate or a polymeric material.
Such an arrangement is depicted schematically in FIG. 1, where an
LED 1 that is arranged to emit blue primary light 2 upon the
application of current is submerged in a commercially available LED
encapsulant 3 in which is embedded a plurality of quantum
dot-containing polymeric beads 4, 5; a proportion of the beads 4
containing quantum dots that emit red secondary light 6 upon
excitation by the blue primary light from the LED 1, and the
remainder containing quantum dots 4 that emit green secondary light
7 upon excitation by the blue primary light from the LED 1.
In the Comparative Example below, an LED-based light-emitting
device incorporating a formulation according to the first aspect of
the present invention is tested against a light-emitting device
incorporating "naked" quantum dots embedded directly in an LED
encapsulant analogous to prior art methods. The device
incorporating the formulation according to embodiments of the
present invention was observed to perform significantly better than
the prior art device in that the quantum dot-containing beads
(QD-bead) were more robust in the silicone LED encapsulent used and
the device exhibited an enhanced LED lifetime.
The term "beads" is used for convenience and is not intended to
impose any particular size or shape limitation. Thus, for example,
the beads may be spherical but other configurations are possible,
such as disc- or rod-like. Where reference is made herein to
"microbeads" this is intended to refer to "beads" as defined above
having a dimension on the micron scale.
The nanoparticle-containing optically transparent medium is
provided in the form of a plurality of discrete, i.e., separate or
distinct, microbeads. For the avoidance of doubt, reference to
microbeads as being "discrete" is not intended to exclude composite
materials formed by aggregations of microbeads, since even in such
materials each microbead retains its original bead-like structure,
despite being in contact with one or more other microbeads. By
pre-loading small microbeads that can range in size from 50 nm to
500 .mu.m, or more preferably 25 nm to 0.1 mm, or more preferably
still 20 nm to 0.5 mm in diameter, with quantum dots, then
incorporating one or more of these quantum dot-containing beads
into an LED encapsulation material on a UV or blue LED, it becomes
a simple process to change, in a controllable and reproducible
manner, the color of the light emitted by the LED device. Moreover,
it has been shown that this approach is typically simpler than
attempting to incorporate the quantum dots directly into an LED
encapsulate (for example, a silicone, an epoxy, a (meth)acrylate, a
polymeric material or the like) in terms of ease of color
rendering, processing, and reproducibility and offers greater
quantum dot stability to photo-oxidation.
This approach may lead to better processing; the quantum
dot-containing beads can be made to the same size as the currently
employed YAG phosphor material which range from 10 to 100 .mu.m and
can thus be supplied to commercial manufacturers in a similar form
to that of the current commercially used phosphor material.
Moreover, the quantum dot-containing beads are in a form that is
compatible with the existing LED fabrication infrastructure.
With the advantage of very little or no loss of quantum dot quantum
yield (QY) in processing, this new approach may lead to less loss
of quantum efficiency than when formulating the quantum dots
directly into a LED encapsulation medium. Because there is very
little or no loss of quantum yield, it is easier to color render
and less binning is required. It has been shown that when
formulating quantum dots directly into an encapsulation medium
using prior art methods, color control is very difficult due to
quantum dot re-absorption or loss of quantum yield and shifting of
the PL max position. Moreover batch to batch, i.e., device to
device, reproducibility is very difficult or impossible to achieve.
By pre-loading the quantum dots into one or more beads, the color
of the light emitted by the device is easier to control and is more
reproducible.
By first incorporating known amounts of quantum dots into beads
before embedding the beads into the LED encapsulant, migration of
moisture and oxygen is eliminated or reduced, thereby eliminating
or at least reducing these hurdles to industrial production.
A second aspect of the present invention provides a method of
preparing a formulation for use in the fabrication of a
light-emitting device, the method including incorporating a
population of semiconductor nanoparticles into a plurality of
discrete microbeads comprised of an optically transparent medium,
and embedding the nanoparticle-containing medium into a host
light-emitting diode encapsulation material.
A third aspect of the present invention provides a light-emitting
device including a primary light source in optical communication
with a formulation comprising a population of semiconductor
nanoparticles incorporated into a plurality of discrete microbeads
comprised of an optically transparent medium, the
nanoparticle-containing medium being embedded in a host
light-emitting diode encapsulation medium.
A fourth aspect of the present invention provides a method of
fabricating a light-emitting device, the method including providing
a population of semiconductor nanoparticles in a plurality of
discrete microbeads comprised of an optically transparent medium,
embedding the nanoparticle-containing medium in a host
light-emitting diode encapsulation material to produce a
nanoparticle-containing formulation, and depositing the formulation
on a primary light source such that the primary light source is in
optical communication with the population of semiconductor
nanoparticles.
The optically transparent medium that is to contain the
semiconductor nanoparticles, preferably in the form of
nanoparticle-containing beads as hereinbefore defined, may be made
in the form of a resin, polymer, monolith, glass, sol gel, epoxy,
silicone, (meth)acrylate or the like using any appropriate method.
It is preferred that the resulting nanoparticle-containing medium
is suitably compatible with the LED encapsulant to enable the
nanoparticle-containing medium to be embedded within the
encapsulant such that the chemical and physical structure of the
resulting composite material (i.e., the LED encapsulant with
nanoparticle-containing medium embedded therein) remains
substantially unchanged during further processing to incorporate
the composite into a light-emitting device and during operation of
the resulting device over a reasonable lifetime for the device.
Suitable optically transparent media include:
poly(methyl(meth)acrylate) (PMMA); poly(ethylene glycol
dimethacrylate) (PEGMA); poly(vinyl acetate) (PVA); poly(divinyl
benzene) (PDVB); poly(thioether); silane monomers; epoxy polymers;
and combinations thereof.
A particularly preferred optically transparent medium that has been
shown to exhibit excellent processibility and light-emitting device
performance includes a copolymer of PMMA, PEGMA, and PVA, as
described below in Example 1. Other preferred optically transparent
media are exemplified below in Examples 2 to 5, which employ
polystyrene microspheres with divinyl benzene and a thiol
co-monomer; silane monomers (e.g.,
3-(trimethoxysilyl)propylmethacrylate (TMOPMA) and tetramethoxy
silane (TEOS)); and an epoxy polymer (e.g., Optocast.TM. 3553 from
Electronic Materials, Inc., USA).
By incorporating quantum dots into an optically transparent,
preferably clear, stable medium it is possible to protect the
otherwise reactive quantum dots from the potentially damaging
surrounding chemical environment. Moreover, by placing a number of
quantum dots into a single bead, for example in the size range from
20 nm to 500 .mu.m in diameter, the subsequent QD-bead tends to be
more stable than the free "naked" quantum dots to the types of
chemical, mechanical, thermal and photo-processing steps that are
required to incorporate quantum dots in most commercial
applications, such as when employing quantum dots as down
converters in a "QD-solid-state-LED" light-emitting device.
It will be evident to one of skill in the art that the optically
transparent medium may contain any desirable number and/or type of
semiconductor nanoparticles. Thus, the medium may contain a single
type of semiconductor nanoparticle, e.g., CdSe, of a specific size
range, such that the composite material incorporating the
nanoparticles incorporated within the medium emits monochromatic
light of a pre-defined wavelength, i.e., color. The color of the
emitted light may be adjusted by varying the type of semiconductor
nanoparticle material used, e.g., changing the size of the
nanoparticle, the nanoparticle core semiconductor material and/or
adding one or more outer shells of different semiconductor
materials. Moreover, color control can also be achieved by
incorporating different types of semiconductor nanoparticles, for
example, nanoparticles of different size and/or chemical
composition within the optically transparent medium. Furthermore,
the color and color intensity can be controlled by selecting an
appropriate number of semiconductor nanoparticles within the
optically transparent medium. Preferably the medium contains at
least around 1000 semiconductor nanoparticles of one or more
different types, more preferably at least around 10,000, more
preferably at least around 50,000, and most preferably at least
around 100,000 semiconductor nanoparticles of one or more different
types.
The optically transparent medium may be provided in the form of a
plurality of microbeads, some or all of which preferably contain
one or more semiconductor nanoparticles capable of secondary light
emission upon excitation by primary light emitted by a primary
light source (e.g., an LED). It is preferred that the formulation
according to the first aspect of the present invention contains a
population of semiconductor nanoparticles distributed across a
plurality of beads embedded within the LED encapsulant. Any
desirable number of beads may be embedded, for example, the LED
encapsulant may contain 1 to 10,000 beads, more preferably 1 to
5000 beads, and most preferably 5 to 1000 beads.
Some or all of the nanoparticle-containing microbeads may include a
core including a first optically transparent medium and one or more
outer layers or shells of the same or one or more different
optically transparent media deposited on the core. Nanoparticles
may be confined to the core region of the microbeads or may be
dispersed throughout the core and/or one or more of the shell
layers of the microbeads. An example of preparing a core/shell
microbead containing a population of semiconductor nanoparticles is
described below in Example 4.
It should also be appreciated that the LED encapsulant may have
embedded therein one or more types of semiconductor
nanoparticle-containing optically transparent medium. That is, two
or more different types of optically transparent media (one or more
containing the nanoparticles) may be embedded within the LED
encapsulant. In this way, where the population of nanoparticles
contains more than one different type of nanoparticle, the nature
of the optically transparent media can be selected for optimum
compatibility with both the different types of nanoparticles and
the particular LED encapsulant used.
Advantages of quantum dot-containing beads over free quantum dots
include greater stability to air and moisture, greater stability to
photo-oxidation and greater stability to mechanical processing.
Moreover, by pre-loading small microbeads, which can range in size
from a few 50 nm to 500 .mu.m, with quantum dots and then
incorporating one or more of these quantum dot-containing beads
into an LED encapsulation material on a UV or blue LED, a
relatively simple process is provided to change, in a controllable
and reproducible manner, the color of the light emitted by the
LED-based light-emitting device.
In the Comparative Example presented below a light-emitting device
according to an embodiment of the present invention incorporating
QD-beads embedded within an LED encapsulant performs significantly
better than a light-emitting device incorporating "naked" quantum
dots embedded directly in an LED encapsulant analogous to prior art
methods.
Semiconductor Nanoparticles
Any desirable type of semiconductor nanoparticle may be employed in
the formulation of the first aspect of the present invention and
the methods and devices forming the second, third and fourth
aspects of the present invention. In a preferred embodiment of the
formulation according to the first aspect of the present invention
the nanoparticle contains ions, which may be selected from any
desirable group of the periodic table, such as but not limited to
group 11, 12, 13, 14, 15 or 16 of the periodic table. The
nanoparticle may incorporate transition metal ions or d-block metal
ions. It is preferred that the nanoparticles contain first and
second ions with the first ion preferably selected from group 11,
12, 13 or 14 and the second ion preferably selected from group 14,
15 or 16 of the periodic table. The nanoparticles may contain one
or more semiconductor materials such as, for example, CdS, CdSe,
CdTe, ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlP, AlS, AlAs, AlSb, GaN,
GaP, GaAs, GaSb, PbS, PbSe, Si, Ge, MgS, MgSe, MgTe, and
combinations thereof. Moreover, the nanoparticles may be binary,
tertiary or quaternary core, core-shell or core-multi shell, doped
or graded nanoparticles as are known to one of skill in the
art.
Any appropriate method may be employed to produce the semiconductor
nanoparticles employed in the various aspects of the present
invention. The semiconductor nanoparticles are preferably produced
by converting a nanoparticle precursor composition to the material
of the nanoparticles in the presence of a molecular cluster
compound under conditions permitting seeding and growth of the
nanoparticles on the cluster compound. Conveniently, the
nanoparticles incorporate first and second ions and the
nanoparticle precursor composition comprises first and second
nanoparticle precursor species containing the first and second ions
respectively which are combined, preferably in the presence of a
molecular cluster compound, as exemplified below in Synthetic
Methods 1 and 2. The first and second precursor species may be
separate species in the precursor composition or may form part of a
single molecular species containing both the first and second ions.
The method may employ the methodology set out in co-pending
European patent application (Publication No. EP1743054A) and U.S.
patent application Ser. No. 11/579,050, the disclosures of which
are incorporated by reference herein in their entireties. The
molecular cluster compound may contain third and fourth ions. At
least one of the third and fourth ions is preferably different to
the first and second ions contained in the first and second
nanoparticle precursor species respectively. The third and fourth
ions may be selected from any desirable group of the periodic
table, such as but not limited to group 11, 12, 13, 14, 15 or 16 of
the periodic table. The third and/or fourth ion may be a transition
metal ion or a d-block metal ion. Preferably the third ion is
selected from group 11, 12, 13 or 14 and the fourth ion is selected
from group 14, 15 or 16 of the periodic table. By way of example,
the molecular cluster compound may incorporate third and fourth
ions from groups 12 and 16 of the periodic table respectively and
the first and second ions derived from the first and second
nanoparticle precursor species may be taken from groups 13 and 15
of the periodic table respectively as in Synthetic Method 2.
Accordingly, the methods according to the first and second aspects
of the present invention may employ methodology taken from the
co-pending international patent application (Publication No.
WO/2009/016354) and U.S. Pat. No. 7,588,828, the disclosures of
which are incorporated by reference herein in their entireties.
It will be appreciated that during the reaction of the first and
second nanoparticle precursor species, the first nanoparticle
precursor species may be added in one or more portions and the
second nanoparticle precursor species may be added in one or more
portions. The first nanoparticle precursor species is preferably
added in two or more portions. In this case, it is preferred that
the temperature of a reaction mixture containing the first and
second nanoparticle precursor species is increased between the
addition of each portion of the first precursor species.
Additionally or alternatively, the second nanoparticle precursor
species may be added in two or more portions, whereupon the
temperature of a reaction mixture containing the first and second
nanoparticle precursor species may be increased between the
addition of each portion of the second precursor species.
The coordination about the final inorganic surface atoms in any
core, core-shell or core-multi shell, doped or graded nanoparticle
is typically incomplete, with highly reactive non-fully coordinated
atoms acting as "dangling bonds" on the surface of the particle,
which can lead to particle agglomeration. This problem is typically
overcome by passivating (capping) the "bare" surface atoms with
protecting organic groups.
In many cases, the capping agent is the solvent in which the
nanoparticles have been prepared, and consists of a Lewis base
compound, or a Lewis base compound diluted in an inert solvent such
as a hydrocarbon. There is a lone pair of electrons on the Lewis
base capping agent that are capable of a donor type coordination to
the surface of the nanoparticle and include mono- or multi-dentate
ligands such as phosphines (trioctylphosphine, triphenylphosphine,
t-butylphosphine etc.), phosphine oxides (trioctylphosphine oxide,
triphenylphosphine oxide etc.), alkyl phosphonic acids,
alkyl-amines (hexadecylamine, octylamine etc.), aryl-amines,
pyridines, long chain fatty acids and thiophenes but is, as one
skilled in the art will know, not restricted to these
materials.
In addition to the outermost layer of organic material or sheath
material (capping agent) helping to inhibit
nanoparticle-nanoparticle aggregation, this layer can also protect
the nanoparticles from their surrounding electronic and chemical
environments, and provide a means of chemical linkage to other
inorganic, biological or organic material, whereby the functional
group is pointing away from the nanoparticle surface and is
available to bond/react/interact with other available molecules,
such as amines, alcohols, carboxylic acids, esters, acid chloride,
anhydrides, ethers, alkyl halides, amides, alkenes, alkanes,
alkynes, allenes, amino acids, azides, groups etc. but is, as one
skilled in the art will know, not limited to these functionalised
molecules. The outermost layer (capping agent) of a quantum dot can
also consist of a coordinated ligand that processes a functional
group that is polymerisable and can be used to form a polymer layer
around the nanoparticle. The outermost layer can also consist of
organic units that are directly bonded to the outermost inorganic
layer such as via a disulphide bond between the inorganic surface
(e.g., ZnS) and a thiol capping molecule. These can also possess
additional functional group(s), not bonded to the surface of the
particle, which can be used to form a polymer around the particle,
or for further reaction/interaction/chemical linkage.
An example of a material to which nanoparticle surface binding
ligands may be linked is an optically transparent medium compatible
with an LED encapsulant material. There are a number of approaches
to incorporate semiconductor nanoparticles, such as quantum dots,
into optically transparent media by pre-coating the nanoparticles
with ligands that are compatible in some way with the material of
the optically transparent media. By way of example, in the
preferred embodiment where the nanoparticles are to be incorporated
into polymeric beads, the nanoparticles can be produced so as to
possess surface ligands which are polymerizable, hydrophobic or
hydrophilic or by being positively or negatively charged or by
being functionalised with a reactive group capable of associating
with the polymer of the polymeric beads either by chemical
reaction/covalent linkage/non-covalent interaction
(interchelation).
It has been determined that it is possible to take quantum dots
capped with polymerisable ligands or a capping agent, such as an
amine or phosphine, and incorporate these quantum dots into polymer
beads, which can be embedded within a host LED encapsulant and then
deposited onto a solid-state LED chip to form a quantum dot-based
light-emitting device. Accordingly, the second aspect of the
present invention provides a method of preparing a formulation for
use in the fabrication of a light-emitting device, the method
including incorporating a population of semiconductor nanoparticles
into an optically transparent medium and embedding the
nanoparticle-containing medium into a host light-emitting diode
encapsulation material.
Incorporating Quantum Dots into Beads
Considering the initial step of incorporating quantum dots into
beads, a first option is to incorporate the quantum dots directly
into the polymer matrices of resin beads. A second option is to
immobilise the quantum dots in polymer beads through physical
entrapment. It is possible to use these methods to make a
population of beads that contain just a single type of quantum dot
(e.g., one color) by incorporating a single type of quantum dot
into the beads. Alternatively, it is possible to construct beads
that contain 2 or more types of quantum dots (e.g., two or more
colors) by incorporating a mixture of two or more types of quantum
dot (e.g., material and/or size) into the beads. Such mixed beads
can then be combined in any suitable ratio to emit any desirable
color of secondary light following excitation by the primary light
emitted by the primary light source (e.g., LED). This is
exemplified in FIGS. 6 to 8 that schematically show QD-bead
light-emitting devices including respectively: a) multi-colored,
multiple quantum dot types in each bead such that each bead emits
white secondary light; b) multi-colored, multiple quantum dot types
in different beads such that each bead contains a single quantum
dot type emitting a single color, a mixture of the beads combining
to produce white secondary light; and c) singly colored, single
quantum dot type in all beads such that a mixture of the beads
emits a single color of secondary light, e.g., red.
Incorporating Quantum Dots Beads During Bead Formation
With regard to the first option, by way of example,
hexadecylamine-capped CdSe-based semiconductor nanoparticles can be
treated with at least one, more preferably two or more
polymerisable ligands (optionally one ligand in excess) resulting
in the displacement of at least some of the hexadecylamine capping
layer with the polymerisable ligand(s). The displacement of the
capping layer with the polymerisable ligand(s) can be accomplished
by selecting a polymerisable ligand or ligands with structures
similar to that of trioctylphosphine oxide (TOPO), which is a
ligand with a known and very high affinity for CdSe-based
nanoparticles. It will be appreciated that this basic methodology
may be applied to other nanoparticle/ligand pairs to achieve a
similar effect. That is, for any particular type of nanoparticle
(material and/or size), it is possible to select one or more
appropriate polymerisable surface binding ligands by choosing
polymerisable ligands comprising a structural motif which is
analogous in some way (e.g., has a similar physical and/or chemical
structure) to the structure of a known surface binding ligand. Once
the nanoparticles have been surface-modified in this way, they can
then be added to a monomer component of a number of microscale
polymerisation reactions to form a variety of quantum
dot-containing resins and beads. A preferred embodiment of the
second aspect of the present invention comprises the polymerisation
of one or more polymerisable monomers from which the optically
transparent medium is to be formed in the presence of at least a
portion of the semiconductor nanoparticles to be incorporated into
the optically transparent medium. The resulting materials
incorporate the quantum dots covalently and appear highly colored
even after prolonged periods of Soxhlet extraction.
Examples of polymerisation methods that may be used to construct
quantum dot-containing beads include, e.g., suspension, dispersion,
emulsion, living, anionic, cationic, RAFT, ATRP, bulk, ring closing
metathesis and ring opening metathesis. Initiation of the
polymerisation reaction may be caused by any suitable method which
causes the monomers to react with one another, such as by the use
of free radicals, light, ultrasound, cations, anions, or heat. A
preferred method is suspension polymerisation involving thermal
curing of one or more polymerisable monomers from which the
optically transparent medium is to be formed. The polymerisable
monomers preferably include methyl(meth)acrylate, ethylene glycol
dimethacrylate and vinyl acetate. This combination of monomers has
been shown to exhibit excellent compatibility with existing
commercially available LED encapsulants and has been used to
fabricate a light-emitting device exhibiting significantly improved
performance compared to a device prepared using essentially prior
art methodology. Other preferred polymerisable monomers are epoxy
or polyepoxide monomers, which may be polymerised using any
appropriate mechanism, such as curing with ultraviolet
irradiation.
Quantum dot-containing microbeads can be produced by dispersing a
known population of quantum dots within a polymer matrix, curing
the polymer and then grinding the resulting cured material. This is
particularly suitable for use with polymers that become relatively
hard and brittle after curing, such as many common epoxy or
polyepoxide polymers (e.g., Optocast.TM. 3553 from Electronic
Materials, Inc., USA).
Quantum dot-containing beads may be generated simply by adding
quantum dots to the mixture of reagents used to construct the
beads. In some instances quantum dots (nascent quantum dots) may be
used as isolated from the reaction employed to synthesise them and
are thus generally coated with an inert outer organic ligand layer.
In an alternative procedure a ligand exchange process may be
carried out prior to the bead forming reaction. Here one or more
chemically reactive ligands (for example this might be a ligand for
the quantum dots that also contains a polymerisable moiety) is
added in excess to a solution of nascent quantum dots coated in an
inert outer organic layer. After an appropriate incubation time,
the quantum dots are isolated, for example by precipitation and
subsequent centrifugation, washed and then incorporated into the
mixture of reagents used in the bead forming reaction/process.
Both quantum dot incorporation strategies will result in
statistically random incorporation of the quantum dots into the
beads and thus the polymerisation reaction may result in beads
containing statistically similar amounts of the quantum dots. It
will be obvious to one of skill in the art that bead size can be
controlled by the choice of polymerisation reaction used to
construct the beads and additionally once a polymerisation method
has been selected bead size can also be controlled by selecting
appropriate reaction conditions, e.g., in a suspension
polymerisation reaction by stirring the reaction mixture more
quickly to generate smaller beads. Moreover the shape of the beads
can be readily controlled by choice of procedure in conjunction
with whether or not the reaction is carried out in a mould. The
composition of the beads can be altered by changing the composition
of the monomer mixture from which the beads are constructed.
Similarly the beads can also be cross-linked with varying amounts
of one or more cross-linking agents (e.g., divinyl benzene). If
beads are constructed with a high degree of cross-linking, e.g.,
greater than 5 mol % cross-linker, it may be desirable to
incorporate a porogen (e.g., toluene or cyclohexane) during the
reaction used to construct the beads. The use of a porogen in such
a way leaves permanent pores within the matrix constituting each
bead. These pores may be sufficiently large to allow the ingress of
quantum dots into the bead.
Quantum dots can also be incorporated in beads using reverse
emulsion based techniques, as exemplified below in Examples 3 and
4. The quantum dots may be mixed with precursor(s) to the optically
transparent coating material and then introduced into a stable
reverse emulsion containing, for example, an organic solvent and a
suitable salt. Following agitation, the precursors form microbeads
encompassing the quantum dots, which can then be collected using
any appropriate method, such as centrifugation. If desired, one or
more additional surface layers or shells of the same or a different
optically transparent material can be added prior to isolation of
the quantum dot-containing beads by addition of further quantities
of the requisite shell layer precursor material(s) as exemplified
in Example 4.
Incorporating Quantum Dots into Prefabricated Beads
With respect to the second option for incorporating quantum dots
into beads, the quantum dots can be immobilised in polymer beads
through physical entrapment. For example, a solution of quantum
dots in a suitable solvent (e.g., an organic solvent) can be
incubated with a sample of polymer beads. Removal of the solvent
using any appropriate method results in the quantum dots becoming
immobilised within the matrix of the polymer beads. The quantum
dots remain immobilised in the beads unless the sample is
resuspended in a solvent (e.g., organic solvent) in which the
quantum dots are freely soluble. Optionally, at this stage the
outside of the beads can be sealed. A further preferred embodiment
of the second aspect of the present invention comprises the
physical attachment of at least a portion of the semiconductor
nanoparticles to prefabricated polymeric beads. The attachment may
be achieved by immobilisation of the portion of the semiconductor
nanoparticles within the polymer matrix of the prefabricated
polymeric beads or by chemical, covalent, ionic, or physical
connection between the portion of semiconductor nanoparticles and
the prefabricated polymeric beads. In a particularly preferred
embodiment the prefabricated polymeric beads comprise polystyrene,
polydivinyl benzene and a polythiol.
Quantum dots may be irreversibly incorporated into prefabricated
beads in a number of ways, e.g., chemical, covalent, ionic,
physical (e.g., by entrapment) or any other form of interaction. If
prefabricated beads are to be used for the incorporation of quantum
dots, the solvent accessible surfaces of the bead may be chemically
inert (e.g., polystyrene) or alternatively they may be chemically
reactive/functionalised (e.g., Merrifield's Resin). The chemical
functionality may be introduced during the construction of the
bead, for example by the incorporation of a chemically
functionalised monomer, or alternatively chemical functionality may
be introduced in a post bead construction treatment, for example by
conducting a chloromethylation reaction. Additionally, chemical
functionality may be introduced by a post bead construction
polymeric graft or other similar process whereby chemically
reactive polymer(s) are attached to the outer layers/accessible
surfaces of the bead. It will be obvious to one of skill in the art
that more than one such post construction derivatisation process
may be carried out to introduce chemical functionality onto/into
the bead.
As with quantum dot incorporation into beads during the bead
forming reaction, i.e., the first option described above, the
pre-fabricated beads can be of any shape, size and composition and
may have any degree of cross-linker and may contain permanent pores
if constructed in the presence of a porogen. Quantum dots may be
imbibed into the beads by incubating a solution of quantum dots in
an organic solvent and adding this solvent to the beads. The
solvent must be capable of wetting the beads and in the case of
lightly crosslinked beads, preferably 0-10% crosslinked and most
preferably 0-2% crosslinked the solvent should cause the polymer
matrix to swell in addition to solvating the quantum dots. Once the
quantum dot-containing solvent has been incubated with the beads,
it is removed, for example by heating the mixture and causing the
solvent to evaporate and the quantum dots to become embedded in the
polymer matrix constituting the bead or alternatively by the
addition of a second solvent in which the quantum dots are not
readily soluble but which mixes with the first solvent causing the
quantum dots to precipitate within the polymer matrix constituting
the beads. Immobilisation may be reversible if the bead is not
chemically reactive or else if the bead is chemically reactive the
quantum dots may be held permanently within the polymer matrix, by
chemical, covalent, ionic, or any other form of interaction.
Incorporation of Quantum Dots into Sol-Gels to Produce Glass
Optically transparent media that are sol-gels and glasses that are
intended to incorporate quantum dots may be formed in an analogous
fashion to the method used to incorporate quantum dots into beads
during the bead forming process as described above. For example, a
single type of quantum dot (e.g., one color) may be added to the
reaction mixture used to produce the sol-gel or glass.
Alternatively, two or more types of quantum dot (e.g., two or more
colors) may be added to the reaction mixture used to produce the
sol-gel or glass. The sol-gels and glasses produced by these
procedures may have any shape, morphology or 3-dimensional
structure. For example, the particles may be spherical, disc-like,
rod-like, ovoid, cubic, rectangular or any of many other possible
configurations.
Incorporating Quantum Dot-Beads into LED Encapsulant
It is a significant advantage of the present invention that quantum
dot-beads (QD-beads) produced as described above can be
incorporated into commercially available LED encapsulant materials
simply by weighing the desired amount of QD-bead material and
adding this to the desired amount of LED encapsulant material.
Preferably the resulting composite is mixed thoroughly to provide a
homogeneous mixture. Thus, in a preferred embodiment of the second
aspect of the present invention, the nanoparticle-containing medium
is embedded into the host light-emitting diode encapsulation
material by mixing the nanoparticle-containing medium with the
encapsulation material until the nanoparticle-containing medium is
substantially evenly dispersed throughout the encapsulation medium.
The QD-bead-LED-encapsulant composite may then be dispensed onto a
commercially available LED and cured according to the normal curing
procedure for the particular LED-encapsulant used. The QD-bead-LED
encapsulant formulation according to the first aspect of the
present invention thus provides a simple and straightforward way of
facilitating the fabrication of next generation, higher performance
light-emitting devices using, as far as possible, standard
commercially available materials and methods.
LED Encapsulating Materials
Any existing commercially available LED encapsulant may be used in
connection with the various aspects of the present invention.
Preferred LED encapsulants include silicones, epoxies,
(meth)acrylates and other polymers, although it will be appreciated
by one of skill in the art that further options are available, such
as but not limited to silica glass, silica gel, siloxane, sol gel,
hydrogel, agarose, cellulose, epoxy, polyether, polyethylene,
polyvinyl, poly-diacetylene, polyphenylene-vinylene, polystyrene,
polypyrrole, polyimide, polyimidazole, polysulfone, polythiophene,
polyphosphate, poly(meth)acrylate, polyacrylamide, polypeptide,
polysaccharide, and combinations thereof.
LED encapsulants that may be used in the various aspects of the
present invention include, but are not limited to, UV curable
encapsulants and heat curable encapsulants, including encapsulants
that require one or more catalysts to support the curing process.
Specific examples of commercially available silicone encapsulants
that are suitable for use with aspects of the present invention may
be, for example, SCR1011, SCR1012, SCR1016, and/or LPS-3412 (all
available from Shin Etsu) and examples of suitable epoxy
encapsulents may be, for exampled, Pacific Polytech PT1002, Fine
Polymers Epifine EX-1035A, and/or Fine Polymers Epifine X-1987.
Color Indexing
The color of the light output from the QD-bead-LED (the "secondary
light") can be measured using a spectrometer. The spectral output
(mW/nm) can then be processed mathematically so that the particular
color of the light-emitting device can be expressed as color
coordinates on a chromaticity diagram, for example the 2.degree.
CIE 1931 chromaticity diagram (see FIG. 4).
The 2.degree. CIE 1931 chromaticity coordinates for a particular
spectrum can be calculated from the spectral power distribution and
the CIE 1931 color matching functions x, y, z (see FIG. 5). The
corresponding tristimulus values can be calculated thus
X=.intg.pxd.lamda. Y=.intg.pyd.lamda. Z=.intg.pzd.lamda.
Where p is the spectral power, and x, y and z are the color
matching functions.
From X, Y, and Z the chromaticity coordinates x, y can be
calculated according to
.times..times..times..times..times. ##EQU00001##
Using x, y as the coordinates, a two-dimensional chromaticity
diagram (the CIE 1931 color space diagram) can be plotted which is
analogous to the exemplary diagram depicted in FIG. 4.
Color Rendering
Color rendering describes the ability of a light source to
illuminate objects such that they appear the correct color when
compared to how they appear when illuminated by a reference light
source. Usually the reference light source is a tungsten filament
bulb which is assigned a color rendering index (CRI) of 100. To be
acceptable for general lighting, a white light-emitting device
source is required to have a CRI>80. An example of poor color
rendering is the sodium street lamp that has very poor color
rendering capability, i.e., it is difficult to distinguish a red
car from a yellow car illuminated by a sodium lamp; in the dark
under a sodium lamp they both appear grey.
Embodiments of the present invention provide a light-emitting
device comprising a population of quantum dots incorporated into an
optically transparent medium (e.g., polymeric beads) which are
embedded within a host light-emitting diode (LED) encapsulation
material/medium (e.g., epoxy resin, silicone, acrylate, etc). The
quantum dots within the optically transparent medium are in optical
communication with a primary solid-state photon/light source (e.g.,
an LED, laser, arc lamp or black-body light source) such that, upon
excitation by primary light from the primary light source, the
quantum dots within the optically transparent medium emit secondary
light of a desired color. The required intensities and emission
wavelengths of the light emitted from the device itself can be
selected according to appropriate mixing of the color of the
primary light with that of the secondary light(s) produced from the
down conversion of the primary light by the quantum dots. Moreover,
the size (and thus emission) and number of each type of quantum dot
within the optically transparent medium can be controlled, as can
the size, morphology and constituency of the optically transparent
medium, such that subsequent mixing of the quantum dot-containing
media allows light of any particular color and intensity to be
produced.
It will be appreciated that the overall light emitted from the
device may consist of effectively just the light emitted from the
quantum dots, i.e., just the secondary light, or a mixture of light
emitted from the quantum dots and light emitted from the
solid-state/primary light source, i.e., a mixture of the primary
and secondary light. Color mixing of the quantum dots can be
achieved either within the quantum dot-containing media (e.g.,
within each bead in a population of beads such that each bead
contains a number of different size/color emitting quantum dots) or
a mixture of differently colored optically transparent media (e.g.,
beads) with all the quantum dots within a specific medium being the
same size/color (e.g., some beads containing all green quantum dots
and others containing all red quantum dots).
EXAMPLES
Examples 1 to 5 below describe the preparation of quantum
dot-containing formulations for use in the fabrication of new,
improved quantum dot-based light-emitting devices in accordance
with embodiments of the present invention. In the Comparative
Example, a device in accordance with an embodiment of the present
invention is tested against a device based on prior art principles
using the same type of quantum dots to compare the performance of
the two devices. Two methods for producing quantum dots suitable
for incorporation into the formulations are first set out in the
Synthetic Methods section below.
Synthetic Methods
Method 1
CdSe/ZnS hexadecylamine-capped quantum dots were prepared as
described below for subsequent processing into a
quantum-dot-containing formulation for use in the fabrication of a
light-emitting device in accordance with embodiments of the present
invention.
Preparation of CdSe-HDA Capped Core Quantum Dots
HDA (500 g) was placed in a three-neck round bottomed flask and
dried and degassed by heating to 120.degree. C. under a dynamic
vacuum for >1 hour. The solution was then cooled to 60.degree.
C. To this was added 0.718 g of
[HNEt.sub.3].sub.4[Cd.sub.10Se.sub.4(SPh).sub.16] (0.20 mmols). In
total 42 mmols, 22.0 ml of TOPSe and 42 mmols, (19.5 ml, 2.15 M) of
Me.sub.2Cd.TOP was used. Initially 4 mmol of TOPSe and 4 mmols of
Me.sub.2Cd.TOP were added to the reaction at room temperature and
the temperature increased to 110.degree. C. and allowed to stir for
2 hours. The reaction was a deep yellow color. The temperature was
progressively increased at a rate of .about.1.degree. C./5 min with
equimolar amounts of TOPSe and Me.sub.2Cd.TOP being added dropwise.
The reaction was stopped when the PL emission maximum had reached
.about.600 nm, by cooling to 60.degree. C. followed by addition of
300 ml of dry ethanol or acetone. This produced a precipitation of
deep red particles, which were further isolated by filtration. The
resulting CdSe particles were recrystallized by re-dissolving in
toluene followed by filtering through Celite followed by
re-precipitation from warm ethanol to remove any excess HDA,
selenium or cadmium present. This produced 10.10 g of HDA capped
CdSe nanoparticles. Elemental analysis C=20.88, H=3.58, N=1.29,
Cd=46.43%. Max PL=585 nm, FWHM=35 nm. 38.98 mmols, 93% of
Me.sub.2Cd consumed in forming the quantum dots.
Growth of ZnS Shell to Provide CdSe/ZnS-HDA Capped Core/Shell
Quantum Dots
HDA (800 g) was placed in a three-neck round-bottom flask, and
dried and degassed by heating to 120.degree. C. under a dynamic
vacuum for >1 hour. The solution was then cooled to 60.degree.
C.; to this was added 9.23 g of CdSe nanoparticles that have a PL
maximum emission of 585 nm. The HDA was then heated to 220.degree.
C. To this was added by alternate dropwise addition a total of 20
ml of 0.5 M Me.sub.2Zn.TOP and 0.5 M, 20 ml of sulfur dissolved in
octylamine. Three alternate additions of 3.5, 5.5 and 11.0 ml of
each were made, whereby initially 3.5 ml of sulphur was added
dropwise until the intensity of the PL maximum was near zero. Then
3.5 ml of Me.sub.2Zn.TOP was added dropwise until the intensity of
the PL maximum had reached a maximum. This cycle was repeated with
the PL maximum reaching a higher intensity with each cycle. On the
last cycle, additional precursor was added once the PL maximum
intensity been reached until it was between 5-10% below the maximum
intensity, and the reaction was allowed to anneal at 150.degree. C.
for 1 hour. The reaction mixture was then allowed to cool to
60.degree. C. whereupon 300 ml of dry "warm" ethanol was added,
which resulted in the precipitation of particles. The resulting
CdSe--ZnS particles were dried before re-dissolving in toluene and
filtering through Celite followed by re-precipitation from warm
ethanol to remove any excess HDA. This produced 12.08 g of HDA
capped CdSe--ZnS core-shell nanoparticles. Elemental analysis
C=20.27, H=3.37, N=1.25, Cd=40.11, Zn=4.43%; Max PL 590 nm, FWHM 36
nm.
Method 2
InP quantum dots were prepared as described below which can then be
processed into a quantum-dot-containing formulation for use in the
fabrication of a light-emitting device in accordance with
embodiments of the present invention.
Preparation of InP Core Quantum Dots (500-700 nm Emission)
Di-butyl ester (100 ml) and Myristic acid (10.0627 g) were placed
in a three-neck flask and degassed at 70.degree. C. under vacuum
for one hour. After this period, nitrogen was introduced and the
temperature increased to 90.degree. C. ZnS molecular cluster
[Et.sub.3NH.sub.4][Zn.sub.10S.sub.4(SPh).sub.16] (4.7076 g) was
added and the mixture allowed to stir for 45 minutes. The
temperature was then increased to 100.degree. C. followed by the
dropwise addition of In(MA).sub.3 (1 M, 15 ml) followed by
(TMS).sub.3P (1 M, 15 ml). The reaction mixture was allowed to stir
while increasing the temperature to 140.degree. C. At 140.degree.
C., further dropwise additions of In(MA).sub.3 (1 M, 35 ml) (left
to stir for 5 minutes) and (TMS).sub.3P (1 M, 35 ml) were made. The
temperature was then slowly increased to 180.degree. C. and further
dropwise additions of In(MA).sub.3 (1 M, 55 ml) followed by
(TMS).sub.3P (1 M, 40 ml) were made. By addition of the precursor
in the above manner, nanoparticles of InP could be grown with the
emission maximum gradually increasing from 520 nm up to 700 nm,
whereby the reaction can be stopped when the desired emission
maximum has been obtained and left to stir at this temperature for
half an hour. After this period, the temperature was decreased to
160.degree. C. and the reaction mixture was left to anneal for up
to 4 days (at a temperature between 20-40.degree. C. below that of
the reaction). A UV lamp was also used at this stage to aid in
annealing.
The nanoparticles were isolated by the addition of dried degassed
methanol (approx. 200 ml) via cannula techniques. The precipitate
was allowed to settle and then methanol was removed via cannula
with the aid of a filter stick. Dried degassed chloroform (approx.
10 ml) was added to wash the solid. The solid was left to dry under
vacuum for 1 day. This produced 5.60 g of InP core nanoparticles.
Elemental analysis: max PL=630 nm, FWHM=70 nm.
Post-Operative Treatments
The quantum yields of the InP quantum dots prepared above were
increased by washing with dilute HF acid. The dots were dissolved
in anhydrous degassed fchloroform (.about.270 ml). A 50 ml portion
was removed and placed in a plastic flask, flushed with nitrogen.
Using a plastic syringe, the HF solution was made up by adding 3 ml
of 60% w/w HF in water and adding to degassed THF (17 ml). The HF
was added dropwise over 5 hrs to the InP dots. After addition was
complete the solution was left to stir overnight. Excess HF was
removed by extracting through calcium chloride solution in water
and drying the etched InP dots. The dried dots were re-dispersed in
50 ml chloroform for future use. Max 567 nm, FWHM 60 nm. The
quantum efficiencies of the core materials at this stage range from
25-90%
Growth of a ZnS Shell to Provide InP/ZnS Core/Shell Quantum
Dots
A 20 ml portion of the HF etched InP core particles was dried down
in a 3-neck flask. 1.3 g myristic acid and 20 ml di-n-butyl
sebacate ester was added and degassed for 30 minutes. The solution
was heated to 200.degree. C. then 1.2 g anhydrous zinc acetate was
added and 2 ml 1 M (TMS).sub.2S was added dropwise (at a rate of
7.93 ml/hr) after addition was complete the solution was left to
stir. The solution was kept at 200.degree. C. for 1 hr then cooled
to room temperature. The particles were isolated by adding 40 ml of
anhydrous degassed methanol and centrifuged. The supernatant liquid
was disposed of, and 30 ml of anhydrous degassed hexane was added
to the remaining solid. The solution was allowed to settle for 5
hrs and then re-centrifuged. The supernatant liquid was collected
and the remaining solid was discarded. PL emission peak Max.=535
nm, FWHM=65 nm. The quantum efficiencies of the nanoparticle
core/shell materials at this stage ranged from 35-90%.
Example 1
Incorporation of Quantum Dots into Suspension Polymeric Beads
1% wt/vol polyvinyl acetate (PVA) (aq) solution was prepared by
stirring for 12 hours followed by extensive degassing by bubbling
nitrogen through the solution for a minimum of 1 hour. The
monomers, methyl methacrylate and ethylene glycol dimethacrylate,
were also degassed by nitrogen bubbling and used with no further
purification. The initiator AlBN (0.012 g) was placed into the
reaction vessel and put under three vacuum/nitrogen cycles to
ensure no oxygen was present.
CdSe/ZnS core/shell quantum dots as prepared above in Method 1 were
added to the reaction vessel as a solution in toluene and the
solvent removed under reduced pressure. Degassed methyl
methacrylate (0.98 mL) was then added followed by degassed ethylene
glycol dimethacrylate (0.15 mL). The mixture was then stirred at
800 rpm for 15 minutes to ensure complete dispersion of the quantum
dots within the monomer mixture. The solution of 1% PVA (10 mL) was
then added and the reaction stirred for 10 minutes to ensure the
formation of the suspension. The temperature was then raised to
72.degree. C. and the reaction allowed to proceed for 12 hours.
The reaction mixture was then cooled to room temperature and the
beaded product washed with water until the washings ran clear
followed by methanol (100 mL), methanol/tetrahydrofuran (1:1, 100
mL), tetrahydrofuran (100 mL), tetrahydrofuran/dichloromethane
(1:1, 100 mL), dichloromethane (100 mL),
dichloromethane/tetrahydrofuran (1:1, 100 mL), tetrahydrofuran (100
mL), tetrahydrofuran/methanol (1:1, 100 mL), methanol (100 mL). The
quantum dot-containing beads (QD-beads) were then dried under
vacuum and stored under nitrogen.
Quantum Dot-Bead Light-Emitting Device Fabrication
The quantum dot-containing resin suspension beads prepared above
were transferred into vials under an inert atmosphere. An LED
encapsulant (Shin Etsu SCR1011 or Shin Etsu SCR1016) was then added
and the mixture stirred to ensure good dispersion within the
encapsulating polymer. The encapsulant mixture was then transferred
to a well in an LED chip and cured under an inert atmosphere using
standard conditions for the LED encapsulant used.
Example 2
Adsorbing of Quantum Dots into Prefabricated Beads
Polystyrene microspheres with 1% divinyl benzene (DVB) and 1% thiol
co-monomer were resuspended in toluene (1 mL) by shaking and
sonication. The microspheres were centrifuged (6000 rpm, approx 1
min) and the supernatant decanted. This was repeated for a second
wash with toluene and the pellets then resuspended in toluene (1
mL).
InP/ZnS quantum dots as prepared above in Method 2 were dissolved
(an excess, usually 5 mg for 50 mg of microspheres) in chloroform
(0.5 mL) and filtered to remove any insoluble material. The quantum
dot-chloroform solution was added to the microspheres in toluene
and shaken on a shaker plate at room temperature for 16 hours to
mix thoroughly.
The quantum dot-microspheres were centrifuged to pellet and the
supernatant decanted off, which contained any excess quantum dots
present. The pellet was washed (as above) twice with toluene (2
mL), resuspended in toluene (2 mL), and then transferred directly
to glass sample vials used in an integrating sphere. The glass
vials were pelleted down by placing the vials inside a centrifuge
tube, centrifuging and decanting off excess toluene. This was
repeated until all of the material had been transferred into the
sample vial. A quantum yield analysis was then run directly on the
pellet, wet with toluene.
Quantum Dot-Bead Light-Emitting Device Fabrication
The quantum dot-containing resin microspheres prepared above were
transferred into vials under an inert atmosphere. An LED
encapsulant (Shin Etsu SCR1011 or Shin Etsu SCR1016) was then added
and the mixture stirred to ensure good dispersion within the
encapsulating polymer. The encapsulant mixture was then transferred
to a well in an LED chip and cured under an inert atmosphere using
standard conditions for the LED encapsulant used.
Example 3
Reverse Emulsion Synthesis of Silica Beads Embedded with Quantum
Dots
A solution of InP/ZnS core/shell quantum dots (containing 70 mg of
inorganic material) was subjected to evaporation to remove most of
the quantum dot solvent, which in this case was toluene, and then
mixed with silane monomers (e.g., 0.1 mL of
3-(trimethoxysilyl)propylmethacrylate (TMOPMA) and 0.5 mL of
tetramethoxy silane (TEOS)) until a clear solution was
obtained.
10 mL of degassed cyclohexane/Igepal.TM. CO-520 (CO-520 is
C.sub.9H.sub.19-Ph-(OCH.sub.2CH.sub.2).sub.n--OH where n 5) (18
mL/1.35 g) was prepared in a 50 mL flask and 0.1 mL of 4%
NH.sub.4OH injected to form a stable reverse emulsion.
The quantum dot/silane mixture was then injected into the
cyclohexane/CO-520/NH.sub.4OH mixture. The resulting mixture was
stirred at 500 rpm under N.sub.2 overnight. Silica beads containing
the QDs were collected by centrifugation and washed with
cyclohexane twice. The resulting sediment was then dried under
vacuum.
Quantum Dot-Bead LED Fabrication
Quantum dot-containing silica microbeads prepared as described
above can be mixed with an LED encapsulant (e.g., Shin Etsu SCR1011
or Shin Etsu SCR1016) using sufficient stirring to ensure good
dispersion within the encapsulating polymer. The encapsulant
mixture can then be transferred to a well in an LED chip and cured
under an inert atmosphere using standard conditions for the LED
encapsulant used.
Example 4
Reverse Emulsion Synthesis to Form Core/Shell Structured Silica
Beads with Embedded Quantum Dots
A solution of InP/ZnS core/shell quantum dots (containing 70 mg of
inorganic material) was subjected to evaporation to remove most of
the quantum dot solvent, which in this case was toluene, and then
mixed with silane monomers (e.g., 0.1 mL of
3-(trimethoxysilyl)propylmethacrylate (TMOPMA) and 0.5 mL of
tetramethoxy silane (TEOS)) until a clear solution was
obtained.
10 mL of degassed cyclohexane/Igepal.TM. CO-520 (CO-520 is
C.sub.9H.sub.19-Ph-(OCH.sub.2CH.sub.2).sub.n--OH where n 5) (18
mL/1.35 g) was prepared in a 50 mL flask and 0.1 mL of 4%
NH.sub.4OH injected to form a stable reverse emulsion.
The QD/silane mixture was then injected into the
cyclohexane/CO-520/NH.sub.4OH. The mixture was stirred at 500 rpm
under N.sub.2 overnight.
After 4 hours, another 0.5 mL of TEOS was injected into the
reaction flask and the solution stirred overnight. The next day,
another 0.1 mL of 4% NH.sub.4OH was injected into the flask and
stirred for 3 hours. Silica beads containing the QDs with a further
outermost silica layer were collected by centrifugation and washed
with cyclohexane twice. The resulting sediment was then dried under
vacuum.
Quantum Dot-Bead LED Fabrication
Quantum dot-containing core/shell structured silica microbeads
prepared as described above can be mixed with an LED encapsulant
(e.g., Shin Etsu SCR1011 or Shin Etsu SCR1016) using sufficient
stirring to ensure good dispersion within the encapsulating
polymer. The encapsulant mixture can then be transferred to a well
in an LED chip and cured under an inert atmosphere using standard
conditions for the LED encapsulant used.
Example 5
Epoxy Encapsulation of Cadmium Free Quantum Dot-Polymer Samples
An aliquot of a sample of InP/ZnS (cadmium free) quantum dots
dispersed in polycarbonate polymer beads (30 mg) was placed under
vacuum (-30 Psi) in the antechamber of a glove box (20 min) then
refilled with N.sub.2(g). The antechamber was evacuated (-30 Psi)
and refilled with N.sub.2(g) twice more.
The quantum dot-polymer sample was transferred into the glove box
and an epoxy polymer (e.g., Optocast.TM. 3553 from Electronic
Materials, Inc., USA) (30-90 .mu.L) added followed by
homogenisation.
The sample was irradiated (Hg-lamp, 400 W, 5 min) to cure the epoxy
polymer so as to provide a hard and brittle polymer, which was then
ground into a fine powder to provide epoxy beads containing the
InP/ZnS quantum dots.
Quantum Dot-Bead LED Fabrication
Quantum dot-containing epoxy microbeads prepared as described above
can be mixed with an LED encapsulant (e.g., Shin Etsu SCR1011 or
Shin Etsu SCR1016) using sufficient stirring to ensure good
dispersion within the encapsulating polymer. The encapsulant
mixture can then be transferred to a well in an LED chip and cured
under an inert atmosphere using standard conditions for the LED
encapsulant used.
Comparative Example
Two quantum dot-containing light-emitting devices were fabricated
to compare their performance. One of the devices included CdSe/ZnS
core/shell quantum dots (prepared as in Synthetic Method 1)
incorporated directly into a commercially available LED encapsulant
in accordance with prior art methods. The other device included the
same type of quantum dots (prepared as in Synthetic Method 1) but
with the dots incorporated into polymer beads embedded into the LED
encapsulant in accordance with embodiments of the present invention
(prepared as in Example 1).
The CdSe/ZnS quantum dots used in the comparative tests were
obtained from the same batch, produced as described above in
Synthetic Method 1. To make the prior art device, the quantum dots
were embedded directly into Shin Etsu SCR1011 silicone as the LED
encapsulent resin using standard methods. To make the device
according to an embodiment of the present invention, the quantum
dots were first incorporated into methyl methacrylate/ethylene
glycol dimethacrylate 50% crosslinked beads which were then
embedded into Shin Etsu SCR1011 silicone LED encapsulent resin
using the methodology described above in Example 1.
The prior art LED encapsulant mixture was transferred to a well in
a blue emitting LED chip and cured under an inert atmosphere using
standard conditions for the LED encapsulant used. A similar process
was carried out to fabricate the device according to an embodiment
of the present invention but using the LED encapsulant mixture
containing the quantum dot-containing polymer beads (QD-beads).
Post curing, the two light-emitting devices were tested with a
forward current of 20 mA and then continuously powered at room
temperature at 20 mA. Periodically the photometric properties of
the light-emitting devices were measured while powered with a
forward current of 20 mA.
The graph in FIG. 9 is a plot of efficacy and quantum
dot-photoluminescence intensity expressed as a percentage of the
initial value versus time. It should be noted that efficacy values
for each device do not fall to zero since they include a
contribution from the blue LED underneath the QD (or QD-bead) LED
encapsulant composite. As such, efficacy does not fall to zero
since the blue light from the LED is not diminished by the
photodegradation of the QDs.
As can be seen from the results presented in FIG. 9, the QD-beads
are more robust in the silicone LED encapsulant and provide
enhanced light-emitting device lifetimes, thereby demonstrating the
improved performance of a light-emitting device according to
embodiments of the present invention.
It will be seen that the techniques described herein provide a
basis for improved production of nanoparticle materials. The terms
and expressions employed herein are used as terms of description
and not of limitation, and there is no intention in the use of such
terms of and expressions of excluding any equivalents of the
features shown and described or portions thereof. Instead, it is
recognized that various modifications are possible within the scope
of the invention claimed.
* * * * *